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Abstract:

The present invention is related to palladium complexes having substituted
diarylideneacetone ligands and coupling and polymerization processes
thereof.

Claims:

1. A palladium complex, or salt thereof, having at least one atom of
palladium(o), at least one ligand of Formula Ia, and, optionally, one or
more L1; ##STR00028## wherein:L1 is a ligand;R1, R2,
R3, R4, R5, R6, R7, R8, R9, and
R10 are each independently selected from hydrogen, chloro fluoro,
cyano, nitro, C1-4 alkyl, C1-4 haloalkyl, C1-4 alkoxy,
C1-4 haloalkoxy, C1-4 non-terminal alkenyl, C1-4
non-terminal alkynyl, amino, C1-4 alkylamino, C2-8
dialkylamino, C3-6 cycloalkyl, phenyl, a 5- or 6-membered heteroaryl
ring, a 5- or 6-membered hetercycloalkyl ring, hydroxyl, carboxy,
quaternary salt of C2-8 dialkylamino, HO--S(O)2--, HO--S(O)--,
(HO)2P(O)--, C1-4 alkylcarbonyloxy, C1-4
haloalkylcarbonyloxy, C1-4 alkyloxycarbonyl, C1-4
haloalkyloxycarbonyl, tri(C1-4 alkyl)silyloxy, tri(C1-4
haloalkyl)silyloxy, and C1-4 alkylene, wherein said C1-4
alkylene is substituted by a moiety selected from C1-4 alkoxy,
C1-4 haloalkoxy, carboxy, HO--S(O)2--, HO--S(O)--,
(HO)2P(O)--, quaternary salt of C2-8 dialkylamino, C1-4
alkylcarbonyloxy, C1-4 haloalkylcarbonyloxy, C1-4
alkyloxycarbonyl, and C1-4 haloalkyloxycarbonyl;or two adjacent
groups selected from R1, R2, R3, R4, and R5,
along with the carbons to which they are attached, form a fused phenyl
ring or a 5- or 6-membered heteroaryl ring, each of which is optionally
substituted by 1 to 2 independently selected Ra groups;or two
adjacent groups selected from R6, R7, R8, R9, and
R10, along with the carbons to which they are attached, form a fused
phenyl ring or a 5- or 6-membered heteroaryl ring, each of which is
optionally substituted by 1 to 2 independently selected Rb groups;
andeach Ra and Rb is independently selected from chloro,
fluoro, cyano, nitro, C1-4 alkyl, C1-4 alkoxy, C1-4
haloalkoxy, C1-4 haloalkyl, hydroxyl, carboxy, di(C1-4
alkyl)amino, HO--S(O)2--, HO--S(O)--, (HO)2P(O)--, C1-4
alkylcarbonyloxy, C1-4 haloalkylcarbonyloxy, C1-4
alkyloxycarbonyl, C1-4 haloalkyloxycarbonyl, tri(C1-4
alkyl)silyloxy, and tri(C1-4 haloalkyl)silyloxy;with the five
provisos that:(1) at least one of R1, R2, R3, R4,
R5, R6, R7, R8, R9, and R10 is
independently selected from hydroxyl, carboxy, di(C1-4 alkyl)amino,
HO--S(O)2--, HO--S(O)--, (HO)2P(O)--, C1-4
alkylcarbonyloxy, C1-4 haloalkylcarbonyloxy, C1-4
alkyloxycarbonyl, C1-4 haloalkyloxycarbonyl, tri(C1-4
alkyl)silyloxy, tri(C1-4 haloalkyl)silyloxy, and C1-4 alkylene,
wherein said C1-4 alkylene is substituted by a moiety selected from
carboxy, HO--S(O)2--, HO--S(O)--, (HO)2P(O)--, quaternary salt
of C2-8 dialkylamino, C1-4 alkylcarbonyloxy, C1-4
haloalkylcarbonyloxy, C1-4 alkyloxycarbonyl, and C1-4
haloalkyloxycarbonyl; and(2) if one of R1, R2, R3,
R4, and R5 is selected from C3-6 cycloalkyl, phenyl, a 5-
or 6-membered heteroaryl ring, and a 5- or 6-membered hetercycloalkyl
ring; then: (a) the remaining R1, R2, R3, R4, and
R5 are not selected from C3-6 cycloalkyl, phenyl, a 5- or
6-membered heteroaryl ring, and a 5- and 6-membered hetercycloalkyl ring;
and (b) the remaining R1, R2, R3, R4, and R5
adjacent groups, along with the carbons to which they are attached, do
not form a fused phenyl ring or a 5- or 6-membered heteroaryl ring, each
of which is optionally substituted by 1 to 2 Ra independently
selected groups; and(3) if one of R6, R7, R8, R9, and
R10 is selected from C3-6 cycloalkyl, phenyl, a 5- or
6-membered heteroaryl ring, or a 5- or 6-membered hetercycloalkyl ring;
then (a) the remaining R6, R7, R8, R9, and R10
groups are not selected from C3-6 cycloalkyl, phenyl, a 5- or
6-membered heteroaryl ring, and a 5- and 6-membered hetercycloalkyl ring;
and (b) the remaining R6, R7, R8, R9, and R10
adjacent groups, along with the carbons to which they are attached, do
not form a fused phenyl ring or a 5- or 6-membered heteroaryl ring, each
of which is optionally substituted by 1 to 2 Rb independently
selected groups; and(4) if two adjacent groups selected from R1,
R2, R3, R4, and R5, along with the carbons to which
they are attached, form a fused phenyl ring or a 5- or 6-membered
heteroaryl ring, each of which is optionally substituted by 1 to 2
Ra independently selected groups; then: (a) the remaining R1,
R2, R3, R4, and R5 groups are not selected from
C3-6 cycloalkyl, phenyl, a 5- or 6-membered heteroaryl ring, and a
5- or 6-membered hetercycloalkyl ring; and (b) the remaining R1,
R2, R3, R4, and R5 adjacent groups, along with the
carbons to which they are attached, do not form a fused phenyl ring or a
5- or 6-membered heteroaryl ring, each of which is optionally substituted
by 1 to 2 Ra independently selected groups; and(5) if two adjacent
groups selected from R6, R7, R8, R9, and R10,
along with the carbons to which they are attached, form a fused phenyl
ring or a 5- or 6-membered heteroaryl ring, each of which is optionally
substituted by 1 to 2 Rb independently selected groups; then: (a)
the remaining R6, R7, R8, R9, and R10 groups are
not selected from C3-6 cycloalkyl, phenyl, a 5- or 6-membered
heteroaryl ring, and a 5- or 6-membered hetercycloalkyl ring; and (b) the
remaining R6, R7, R8, R9, and R10 adjacent
groups, along with the carbons to which they are attached, do not form a
fused phenyl ring or a 5- or 6-membered heteroaryl ring, each of which is
optionally substituted by 1 to 2 Rb independently selected groups.

2. (canceled)

3. A palladium complex according to claim 1, wherein at least of one of
R1, R2, R3, R4, and R5 and at least one of
R6, R7, R8, R9, and R10 are each independently
selected from hydroxyl, carboxy, and HO--S(O).sub.2--.

4. A palladium complex according to claim 1, wherein at least of one of
R1, R2, R3, R4, and R5 and at least one of
R6, R7, R8, R9, and R10 are each independently
selected from hydroxyl and carboxy.

5. A palladium complex according to claim 1, wherein at least of one of
R1, R2, R3, R4, and R5 and at least one of
R6, R7, R8, R9, and R10 are hydroxyl.

6. (canceled)

7. A palladium complex according to claim 1 wherein at least of one of
R1, R2, R3, R4, and R5 and at least one of
R2 are each C1-4 alkylcarbonyloxy.

17. A palladium complex according to claim 1, wherein each L1 is
tri(o-tolyl)phosphine.

18. A palladium complex according to claim 1, wherein two adjacent groups
selected from R1, R2, R3, R4, and R5, along with
the carbons to which they are attached, do not form a fused phenyl ring
or a 5- or 6-membered heteroaryl ring; andtwo adjacent groups selected
from R6, R7, R8, R9, and R10, along with the
carbons to which they are attached, do not form a fused phenyl ring or a
5- or 6-membered heteroaryl ring.

19. A palladium complex according to claim 1, wherein said complex is of
Formula I: ##STR00029## or salt thereof;wherein:n is from 0 to 2;m is
from 1 to 4;o is from 1 to 2.

65. A palladium complex according to claim 1, which is
tris(4,4'-dihydroxydibenzylideneacetone)dipalladium(0).

66. A palladium complex according to claim 1, wherein at least of one of
R1, R2, R3, R4, and R5 and at least one of
R6, R7, R8, R9, and R10 are hydroxyl; andwherein
four of R1, R2, R3, R4, and R5 are hydrogen and
four of R6, R7, R8, R9, and R10 are hydrogen.

67. A process for preparing a diaromatic compound, comprising mixing a
palladium complex according to claim 1, an aromatic substrate having one
group selected from bromo, iodo, tosylate, benzenesulfonate, mesylate,
triflate, and chloro, an aromatic boronate having one group selected from
boronic acid, boronic ester, and borane, a base, a ligand, an organic
solvent, and water and reacting under conditions sufficient to form the
diaromatic compound.

68. A polymerization process comprising mixing a palladium complex
according to claim 1, an aromatic substrate having two groups
independently selected from bromo, iodo, tosylate, benzenesulfonate,
mesylate, triflate, and chloro, an aromatic diboronate having two groups
independently selected from boronic acid, boronic ester, and borane, a
base, a ligand, a organic solvent and water; and reacting under
conditions sufficient to form a polymer.

Description:

[0001]This application claims the benefit of priority of U.S. Provisional
Application No. 60/982,685, filed Oct. 25, 2007, which is incorporated
herein by reference in its entirety.

[0008]or two adjacent groups selected from R1, R2, R3,
R4, and R5, along with the carbons to which they are attached,
form a fused phenyl ring or a 5- or 6-membered heteroaryl ring, each of
which is optionally substituted by 1 to 2 independently selected Ra
groups;

[0009]or two adjacent groups selected from R6, R7, R8,
R9, and R10, along with the carbons to which they are attached,
form a fused phenyl ring or a 5- or 6-membered heteroaryl ring, each of
which is optionally substituted by 1 to 2 independently selected Rb
groups; and

[0012](2) if one of R1, R2, R3, R4, and R5 is
selected from C3-6 cycloalkyl, phenyl, a 5- or 6-membered heteroaryl
ring, and a 5- or 6-membered hetercycloalkyl ring; then: (a) the
remaining R1, R2, R3, R4, and R5 are not
selected from C3-6 cycloalkyl, phenyl, a 5- or 6-membered heteroaryl
ring, and a 5- and 6-membered hetercycloalkyl ring; and (b) the remaining
R1, R2, R3, R4, and R5 adjacent groups, along
with the carbons to which they are attached, do not form a fused phenyl
ring or a 5- or 6-membered heteroaryl ring, each of which is optionally
substituted by 1 to 2 Ra independently selected groups; and

[0013](3) if one of R6, R7, R8, R9, and R10 is
selected from C3-6 cycloalkyl, phenyl, a 5- or 6-membered heteroaryl
ring, or a 5- or 6-membered hetercycloalkyl ring; then (a) the remaining
R6, R7, R8, R9, and R10 groups are not selected
from C3-6 cycloalkyl, phenyl, a 5- or 6-membered heteroaryl ring,
and a 5- and 6-membered hetercycloalkyl ring; and (b) the remaining
R6, R7, R8, R9, and R10 adjacent groups, along
with the carbons to which they are attached, do not form a fused phenyl
ring or a 5- or 6-membered heteroaryl ring, each of which is optionally
substituted by 1 to 2 Rb independently selected groups; and

[0014](4) if two adjacent groups selected from R1, R2, R3,
R4, and R5, along with the carbons to which they are attached,
form a fused phenyl ring or a 5- or 6-membered heteroaryl ring, each of
which is optionally substituted by 1 to 2 Ra independently selected
groups; then: (a) the remaining R1, R2, R3, R4, and
R5 groups are not selected from C3-6 cycloalkyl, phenyl, a 5-
or 6-membered heteroaryl ring, and a 5- or 6-membered hetercycloalkyl
ring; and (b) the remaining R1, R2, R3, R4, and
R5 adjacent groups, along with the carbons to which they are
attached, do not form a fused phenyl ring or a 5- or 6-membered
heteroaryl ring, each of which is optionally substituted by 1 to 2
Ra independently selected groups; and

[0015](5) if two adjacent groups selected from R6, R7, R8,
R9, and R10, along with the carbons to which they are attached,
form a fused phenyl ring or a 5- or 6-membered heteroaryl ring, each of
which is optionally substituted by 1 to 2 Rb independently selected
groups; then: (a) the remaining R6, R7, R8, R9, and
R10 groups are not selected from C3-6 cycloalkyl, phenyl, a 5-
or 6-membered heteroaryl ring, and a 5- or 6-membered hetercycloalkyl
ring; and (b) the remaining R6, R7, R8, R9, and
R10 adjacent groups, along with the carbons to which they are
attached, do not form a fused phenyl ring or a 5- or 6-membered
heteroaryl ring, each of which is optionally substituted by 1 to 2
Rb independently selected groups.

[0016]In some embodiments, the palladium complexes, or salts thereof, have
Formula I:

[0021]The present invention further provides processes for preparing an
diaromatic compound, comprising mixing a palladium complex of the
invention, or salt thereof, with a composition comprising one or more
materials selected from an aromatic substrate having one group selected
from bromo, iodo, tosylate, benzenesulfonate, mesylate, triflate, and
chloro, an aromatic boronate having one group selected from boronic acid,
boronic ester, and borane, a base, a ligand, an organic solvent, and
water; and

[0022]after the mixing, adding the remaining one or more materials and
reacting under conditions sufficient to form a diaromatic compound.

[0023]The present invention further provides polymerization processes
comprising mixing a palladium complex of the invention, or salt thereof,
with a composition comprising one or more materials selected from an
aromatic substrate having two groups independently selected from bromo,
iodo, tosylate, benzenesulfonate, mesylate, triflate, and chloro, an
aromatic di boronate having two groups independently selected from
boronic acid, boronic ester, and borane, a base, a ligand, an organic
solvent and water; and

[0024]after the mixing, adding the remaining one or more materials and
reacting under conditions sufficient to form a polymer.

[0025]The present invention further provides mixtures comprising an
aromatic substrate having one group selected from bromo, iodo, tosylate,
benzenesulfonate, mesylate, triflate, and chloro, an aromatic boronate
having one group selected from boronic acid, boronic ester, and borane, a
base, water, and a palladium complex of the invention, or salt thereof.

[0026]The present invention further provides mixtures comprising an
aromatic substrate having one group selected from bromo, iodo, tosylate,
benzenesulfonate, mesylate, triflate, and chloro, an aromatic boronate
having one group selected from boronic acid, boronic ester, and borane, a
base, water, and a ligand of Formula Ia, or salt thereof:

[0028]or two adjacent groups selected from R1, R2, R3,
R4, and R5, along with the carbons to which they are attached,
form a fused phenyl ring or a 5- or 6-membered heteroaryl ring, each of
which is optionally substituted by 1 to 2 Ra independently selected
groups;

[0029]or two adjacent groups selected from R6, R7, R8,
R9, and R10, along with the carbons to which they are attached,
form a fused phenyl ring or a 5- or 6-membered heteroaryl ring, each of
which is optionally substituted by 1 to 2 Rb independently selected
groups;

[0031](1) at least one of R1, R2, R3, R4, R5,
R6, R7, R8, R9, and R10 is independently
selected from hydroxyl, carboxy, di(C1-4 alkyl)amino,
HO--S(O)2--, HO--S(O)--, (HO)2P(O)--, and a quaternary salt of
C2-8 dialkylamino; wherein the C1-4 alkylene is substituted by
a moiety selected from carboxy, HO--S(O)2--, HO--S(O)--,
(HO)2P(O)--, and a quaternary salt of C2-8 dialkylamino;

[0032](2) if one of R1, R2, R3, R4, and R5 is
selected from C3-6 cycloalkyl, phenyl, a 5- or 6-membered heteroaryl
ring, and a 5- or 6-membered hetercycloalkyl ring; then: (a) the
remaining R1, R2, R3, R4, and R5 are not
selected from C3-6 cycloalkyl, phenyl, a 5- or 6-membered heteroaryl
ring, and a 5- and 6-membered hetercycloalkyl ring; and (b) the remaining
R1, R2, R3, R4, and R5 adjacent groups, along
with the carbons to which they are attached, do not form a fused phenyl
ring or a 5- or 6-membered heteroaryl ring, each of which is optionally
substituted by 1 to 2 Ra independently selected groups; and

[0033](3) if one of R6, R7, R8, R9, and R10 is
selected from C3-6 cycloalkyl, phenyl, a 5- or 6-membered heteroaryl
ring, or a 5- or 6-membered hetercycloalkyl ring; then (a) the remaining
R6, R7, R8, R9, and R10 groups are not selected
from C3-6 cycloalkyl, phenyl, a 5- or 6-membered heteroaryl ring,
and a 5- and 6-membered hetercycloalkyl ring; and (b) the remaining
R6, R7, R8, R9, and R10 adjacent groups, along
with the carbons to which they are attached, do not form a fused phenyl
ring or a 5- or 6-membered heteroaryl ring, each of which is optionally
substituted by 1 to 2 Rb independently selected groups; and

[0034](4) if two adjacent groups selected from R1, R2, R3,
R4, and R5, along with the carbons to which they are attached,
form a fused phenyl ring or a 5- or 6-membered heteroaryl ring, each of
which is optionally substituted by 1 to 2 Ra independently selected
groups; then: (a) the remaining R1, R2, R3, R4, and
R5 groups are not selected from C3-6 cycloalkyl, phenyl, a 5-
or 6-membered heteroaryl ring, and a 5- or 6-membered hetercycloalkyl
ring; and (b) the remaining R1, R2, R3, R4, and
R5 adjacent groups, along with the carbons to which they are
attached, do not form a fused phenyl ring or a 5- or 6-membered
heteroaryl ring, each of which is optionally substituted by I to 2 Ra
independently selected groups; and

[0035](5) if two adjacent groups selected from R6, R7, R8,
R9, and R10, along with the carbons to which they are attached,
form a fused phenyl ring or a 5- or 6-membered heteroaryl ring, each of
which is optionally substituted by 1 to 2 Rb independently selected
groups; then: (a) the remaining R6, R7, R8, R9, and
R10 groups are not selected from C3-6 cycloalkyl, phenyl, a 5-
or 6-membered heteroaryl ring, and a 5- or 6-membered hetercycloalkyl
ring; and (b) the remaining R6, R7, R8, R9, and
R10 adjacent groups, along with the carbons to which they are
attached, do not form a fused phenyl ring or a 5- or 6-membered
heteroaryl ring, each of which is optionally substituted by 1 to 2
Rb independently selected groups.

[0036]The present invention further provides mixtures comprising an
aromatic substrate having two groups selected from bromo, iodo, tosylate,
benzenesulfonate, mesylate, triflate, and chloro, an aromatic diboronate
having two groups selected from boronic acid, boronic ester, and borane,
a base, water, and a palladium complex of the invention, or salt thereof.

[0037]The present invention further provides mixtures comprising an
aromatic substrate having two groups selected from bromo, iodo, tosylate,
benzenesulfonate, mesylate, triflate, and chloro, an aromatic diboronate
having two groups selected from boronic acid, boronic ester, and borane,
a base, water, and a ligand of Formula Ia:

[0039]or two adjacent groups selected from R1, R2, R3,
R4, and R5, along with the carbons to which they are attached,
form a fused phenyl ring or a 5- or 6-membered heteroaryl ring, each of
which is optionally substituted by to 2 Ra independently selected
groups;

[0040]or two adjacent groups selected from R6, R7, R8,
R9, and R10, along with the carbons to which they are attached,
form a fused phenyl ring or a 5- or 6-membered heteroaryl ring, each of
which is optionally substituted by 1 to 2 Rb independently selected
groups;

[0042](1) at least one of R1, R2, R3, R4, R5,
R6, R7, R8, R9, and R10 is independently
selected from hydroxyl, carboxy, di(C1-4 alkyl)amino,
HO--S(O)2--, HO--S(O)--, (HO)2P(O)--, and a quaternary salt of
C2-8 dialkylamino; wherein the C1-4 alkylene is substituted by
a moiety selected from carboxy, HO--S(O)2--, HO--S(O)--,
(HO)2P(O)--, and a quaternary salt of C2-8 dialkylamino;

[0043](2) if one of R1, R2, R3, R4, and R5 is
selected from C3-6 cycloalkyl, phenyl, a 5- or 6-membered heteroaryl
ring, and a 5- or 6-membered hetercycloalkyl ring; then: (a) the
remaining R1, R2, R3, R4, and R5 are not
selected from C3-6 cycloalkyl, phenyl, a 5- or 6-membered heteroaryl
ring, and a 5- and 6-membered hetercycloalkyl ring; and (b) the remaining
R1, R2, R3, R4, and R5 adjacent groups, along
with the carbons to which they are attached, do not form a fused phenyl
ring or a 5- or 6-membered heteroaryl ring, each of which is optionally
substituted by 1 to 2 Ra independently selected groups; and

[0044](3) if one of R6, R7, R8, R9, and R10 is
selected from C3-6 cycloalkyl, phenyl, a 5- or 6-membered heteroaryl
ring, or a 5- or 6-membered hetercycloalkyl ring; then (a) the remaining
R6, R7, R8, R9, and R10 groups are not selected
from C3-6 cycloalkyl, phenyl, a 5- or 6-membered heteroaryl ring,
and a 5- and 6-membered hetercycloalkyl ring; and (b) the remaining
R6, R7, R8, R9, and R10 adjacent groups, along
with the carbons to which they are attached, do not form a fused phenyl
ring or a 5- or 6-membered heteroaryl ring, each of which is optionally
substituted by 1 to 2 Rb independently selected groups; and

[0045](4) if two adjacent groups selected from R1, R2, R3,
R4, and R5, along with the carbons to which they are attached,
form a fused phenyl ring or a 5- or 6-membered heteroaryl ring, each of
which is optionally substituted by 1 to 2 Ra independently selected
groups; then: (a) the remaining R1, R2, R3, R4, and
R5 groups are not selected from C3-6 cycloalkyl, phenyl, a 5-
or 6-membered heteroaryl ring, and a 5- or 6-membered hetercycloalkyl
ring; and (b) the remaining R1, R2, R3, R4, and
R5 adjacent groups, along with the carbons to which they are
attached, do not form a fused phenyl ring or a 5- or 6-membered
heteroaryl ring, each of which is optionally substituted by 1 to 2
Ra independently selected groups; and

[0046](5) if two adjacent groups selected from R6, R7, R8,
R9, and R10, along with the carbons to which they are attached,
form a fused phenyl ring or a 5- or 6-membered heteroaryl ring, each of
which is optionally substituted by 1 to 2 Rb independently selected
groups; then: (a) the remaining R6, R7, R8, R9, and
R10 groups are not selected from C3-6 cycloalkyl, phenyl, a 5-
or 6-membered heteroatyl ring, and a 5- or 6-membered hetercycloalkyl
ring; and (b) the remaining R6, R7, R8, R9, and
R10 adjacent groups, along with the carbons to which they are
attached, do not form a fused phenyl ring or a 5- or 6-membered
heteroaryl ring, each of which is optionally substituted by 1 to 2
Rb independently selected groups.

[0048]The present invention provides palladium complexes of Formula I,
which are useful for the Suzuki coupling reaction of small molecules and
polymerizations. The complexes of Formula I have at least one moiety
which is either charged or which can form a charged complex under the
basic Suzuki coupling reaction conditions. For example, in some
embodiments, the complex is
tris(4,4'-dihydroxydibenzylideneacetone)dipalladium(0). Without wishing
to be bound by a particular theory, it is believed that the basic
conditions of the catalysis cause the phenolic proton of the ligand to be
deprotonated, thus turning the moderately electron-donating hydroxy group
into a strongly donating oxide. Evidence for the deprotonation (and
subsequent aqueous partitioning) of the dba during the polymerization was
provided by the fact that the aqueous phase turned orange as the reaction
progressed. Since we believed strongly electron-donating groups on the
dibenzylideneacetone (dba) ligands do not provide for stable complexes,
it is thought that this pH switch turns a strong Pd(0) ligand into a weak
one. Further, it is thought that the negative charge on the phenoxide
groups causes the dba ligands to partition into the aqueous phase,
allowing the catalysis to occur unhindered in the organic phase. This has
enabled high yields and the formation of high molecular weight polymers
using Suzuki polymerization.

[0049]Accordingly, in some embodiments, the present invention provides a
palladium complex, or salt thereof, having at least one atom of
palladium(0), at least one ligand of Formula la, and, optionally, one or
more L1;

[0052]or two adjacent groups selected from R1, R2, R3,
R4, and R5, along with the carbons to which they are attached,
form a fused phenyl ring or a 5- or 6-membered heteroaryl ring, each of
which is optionally substituted by 1 to 2 independently selected Ra
groups;

[0053]or two adjacent groups selected from R6, R7, R8,
R9, and R10, along with the carbons to which they are attached,
form a fused phenyl ring or a 5- or 6-membered heteroaryl ring, each of
which is optionally substituted by 1 to 2 independently selected Rb
groups; and

[0056](2) if one of R1, R2, R3, R4, and R5 is
selected from C3-6 cycloalkyl, phenyl, a 5- or 6-membered heteroaryl
ring, and a 5- or 6-membered hetercycloalkyl ring; then: (a) the
remaining R1, R2, R3, R4, and R5 are not
selected from C3-6 cycloalkyl, phenyl, a 5- or 6-membered heteroaryl
ring, and a 5- and 6-membered hetercycloalkyl ring; and (b) the remaining
R1, R2, R3, R4, and R5 adjacent groups, along
with the carbons to which they are attached, do not form a fused phenyl
ring or a 5- or 6-membered heteroaryl ring, each of which is optionally
substituted by 1 to 2 Ra independently selected groups; and

[0057](3) if one of R6, R7, R8, R9, and R10 is
selected from C3-6 cycloalkyl, phenyl, a 5- or 6-membered heteroaryl
ring, or a 5- or 6-membered hetercycloalkyl ring; then (a) the remaining
R6, R7, R8, R9, and R10 groups are not selected
from C3-6 cycloalkyl, phenyl, a 5- or 6-membered heteroaryl ring,
and a 5- and 6-membered hetercycloalkyl ring; and (b) the remaining
R6, R7, R8, R9, and R10 adjacent groups, along
with the carbons to which they are attached, do not form a fused phenyl
ring or a 5- or 6-membered heteroaryl ring, each of which is optionally
substituted by 1 to 2 Rb independently selected groups; and

[0058](4) if two adjacent groups selected from R1, R2, R3,
R4, and R5, along with the carbons to which they are attached,
form a fused phenyl ring or a 5- or 6-membered heteroaryl ring, each of
which is optionally substituted by 1 to 2 Ra independently selected
groups; then: (a) the remaining R1, R2, R3, R4, and
R5 groups are not selected from C3-6 cycloalkyl, phenyl, a 5-
or 6-membered heteroaryl ring, and a 5- or 6-membered hetercycloalkyl
ring; and (b) the remaining R1, R2, R3, R4, and
R5 adjacent groups, along with the carbons to which they are
attached, do not form a fused phenyl ring or a 5- or 6-membered
heteroaryl ring, each of which is optionally substituted by 1 to 2
Ra independently selected groups; and

[0059](5) if two adjacent groups selected from R6, R7, R8,
R9, and R10, along with the carbons to which they are attached,
form a fused phenyl ring or a 5- or 6-membered heteroaryl ring, each of
which is optionally substituted by 1 to 2 Rb independently selected
groups; then: (a) the remaining R6, R7, R8, R9, and
R10 groups are not selected from C3-6 cycloalkyl, phenyl, a 5-
or 6-membered heteroaryl ring, and a 5- or 6-membered hetercycloalkyl
ring; and (b) the remaining R6, R7, R8, R9, and
R10 adjacent groups, along with the carbons to which they are
attached, do not form a fused phenyl ring or a 5- or 6-membered
heteroaryl ring, each of which is optionally substituted by 1 to 2
Rb independently selected groups.

[0060]It is recognized that the one or more palladium(0) metals can form a
coordinate complex with the ligand of Formula Ia and ligand, L1, in
various ratios. In some embodiments, the ratio of the palladium(0) to the
ligand of Formula Ia is 4:2, 3:2, 3:1, or 2:1. In some embodiments, the
ratio of the palladium(0) to the ligand of Formula Ia to L1 is
1:1:1, 1:2:1, or 1:1:2.

[0062]In some embodiments, at least one of the R1, R2, R3,
R4, R5, R6, R7, R8, R9, and R10 group
therefore, is a group is charged or can become charged under the basic
Suzuki coupling reaction conditions, such as hydroxyl, carboxy,
di(C1-4 alkyl)amino, HO--S(O)2--, HO--S(O)--, (HO)2P(O)--,
or quaternary salt of C2-8 dialkylamino group; or a C1-4
alkylene group substituted by a moiety selected from carboxy,
HO--S(O)2--, HO--S(O)--, (HO)2P(O)--, and a quaternary salt of
C2-8 dialkylamino. Alternatively, in some embodiments, the salt form
is isolated and used during the Suzuki coupling reaction or
polymerization.

[0063]In some embodiments, the R1, R2, R3, R4,
R5, R6, R7, R8, R9, and R10 group is a
group which can be hydrolyzed under the Suzuki coupling reaction
conditions to form a group which can then be deprotonated under the basic
conditions, such as a C1-4 alkylcarbonyloxy, C1-4
haloalkylcarbonyloxy, C1-4 alkyloxycarbonyl, C1-4
haloalkyloxycarbonyl, tri(C1-4 alkyl)silyloxy, or tri(C1-4
haloalkyl)silyloxy group; or a C1-4 alkylene group substituted by a
moiety selected from C1-4 alkylcarbonyloxy, C1-4
haloalkylcarbonyloxy, C1-4 alkyloxycarbonyl, C1-4
haloalkyloxycarbonyl, tri(C1-4 alkyl)silyloxy, and tri(C1-4
haloalkyl)silyloxy group. A fluoride base can be used to remove the
ti(C1-4 alkyl)silyloxy, and tri(C1-4 haloalkyl)silyloxy group
to give hydroxy groups which can then be deprotonated with additional
base.

[0066]In some embodiments, at least of one of R1, R2, R3,
R4, and R5 and at least one of R6, R7, R8,
R9, and R10 are each independently selected from hydroxyl,
carboxy, and HO--S(O)2--.

[0067]In some embodiments, at least of one of R1, R2, R3,
R4, and R5 and at least one of R6, R7, R8,
R9, and R10 are each independently selected from hydroxyl and
carboxy.

[0068]In some embodiments, at least of one of R1, R2, R3,
R4, and R5 and at least one of R6, R7, R8,
R9, and R10 are hydroxyl.

[0069]In some embodiments, at least of one of R1, R2, R3,
R4, and R5 and at least one of R6, R7, R8,
R9, and R10 are each independently selected from C1-4
alkylcarbonyloxy, C1-4 haloalkylcarbonyloxy, C1-4
alkyloxycarbonyl, C1-4 haloalkyloxycarbonyl, tri(C1-4
alkyl)silyloxy, and tri(C1-4 haloalkyl)silyloxy.

[0070]In some embodiments, at least of one of R1, R2, R3,
R4, and R5 and at least one of R6, R7, R8,
R9, and R10 are each C1-4 alkylcarbonyloxy.

[0080]In some embodiments, at least of one of R1, R2, R3,
R4, and R5 and at least one of R6, R7, R8,
R9, and R10 are each independently selected from hydroxyl,
carboxy, and HO--S(O)2--; and the remaining R1, R2,
R3, R4, R5, R6, R7, R8, R9, and
R10 groups are selected from hydrogen, hydroxyl, chloro, fluoro,
cyano, nitro, C1-4 alkyl, C1-4 haloalkyl, C1-4 alkoxy, and
C1-4 haloalkoxy.

[0081]In some embodiments, at least of one of R1, R2, R3,
R4, and R5 and at least one of R6, R7, R8,
R9, and R10 are each independently selected from hydroxyl and
carboxy; and the remaining R1, R2, R3, R4, R5,
R6, R7, R8, R9, and R10 groups are each
independently selected from hydrogen, hydroxyl, chloro, fluoro, cyano,
nitro, C1-4 alkyl, C1-4 haloalkyl, C1-4 alkoxy, and
C1-4 haloalkoxy.

[0082]In some embodiments, at least of one of R1, R2, R3,
R4, and R5 and at least one of R6, R7, R8,
R9, and R10 are hydroxyl; and the remaining R1, R2,
R3, R4, R5, R6, R7, R8, R9, and
R10 groups are each independently selected from hydrogen,hydroxyl,
chloro, fluoro, cyano, nitro, C1-4 alkyl, C1-4 haloalkyl,
C1-4 alkoxy, and C1-4 haloalkoxy.

[0105]In some embodiments, at least one of R1, R2, R3,
R4, and R5 are hydrogen and at least one of R6, R7,
R8, R9, and R10 are hydrogen. In some embodiments, at
least two of R1, R2, R3, R4, and R5 are hydrogen
and at least two of R6, R7, R5, R9, and R10 are
hydrogen. In some embodiments, at least three of R1, R2,
R3, R4, and R5 are hydrogen and at least three of R6,
R7, R8, R9, and R10 are hydrogen. In some
embodiments, at least four of R1, R2, R3, R4, and
R5 are hydrogen and at least four of R6, R7, R8,
R9, and R10 are hydrogen.

[0107]In some embodiments, each Ra and Rb is independently
selected from chloro, fluoro, cyano, nitro, C1-4 alkyl, C1-4
alkoxy, C1-4 haloalkoxy, C1-4 haloalkyl, hydroxyl, carboxy,
C1-4 alkylcarbonyloxy, and C1-4 haloalkylcarbonyloxy. In some
embodiments, each Ra and Rb is independently selected from
chloro, fluoro, cyano, nitro, C1-4 alkyl, C1-4 alkoxy,
hydroxyl, and carboxy. In some embodiments, each Ra and Rb is
independently selected from chloro, fluoro, C1-4 alkyl, C1-4
alkoxy, hydroxyl, and carboxy. In some embodiments, each Ra and
Rb is independently selected from C1-4 alkyl, C1-4 alkoxy,
and hydroxyl. In some embodiments, each Ra and Rb is
independently selected from C1-4 alkoxy and hydroxyl.

[0108]In some embodiments, two adjacent groups selected from R1,
R2, R3, R4, and R5, along with the carbons to which
they are attached, do not form a fused phenyl ring or a 5- or 6-membered
heteroaryl ring; and two adjacent groups selected from R6, R7,
R8, R9, and R10, along with the carbons to which they are
attached, do not form a fused phenyl ring or a 5- or 6-membered
heteroaryl ring.

[0109]In some embodiments, the complex is of Formula I:

##STR00007##

or salt thereof,wherein:

[0110]n is from 0 to 2;

[0111]m is from 1 to 4;

[0112]o is from 1 to 2; and

[0113]wherein R1, R2, R3, R4, R5, R6,
R7, R8, R9, R10 Ra, and Rb are defined as
for any of the embodiments described herein.

[0114]In some embodiments, m is 1, n is 1, and o is from 1. In some
embodiments, m is 2, n is 1, and o is from 1. In some embodiments, m is
1, n is 2, and o is from 1. In some embodiments, m is 2, n is 0, and o is
1. In some embodiments, m is 3, n is 0, and o is 1. In some embodiments,
m is 3, n is 0, and o is 2. In some embodiments, m is 4, n is 0, and o is
2. In some embodiments, m is 2, n is 0, and o is 1. In some embodiments,
m is 3 and o is 1. In some embodiments, m is 3 and o is 2. In some
embodiments, m is 4 and o is 2. In some embodiments, m is 2 and o is 1.
In some embodiments, n is 3, m is 0, and o is 1 or 2. In some
embodiments, n is 3 or 4, m is 0, and o is 1 or 2.

[0115]In some embodiments, the palladium complex is selected from:

[0116]tris(4,4'-dihydroxydibenzylideneacetone)dipalladium(0);

[0117]tris(4,4'-dihydroxydibenzylideneacetone)palladium(0);

[0118]bis(4,4'-dihydroxydibenzylideneacetone)palladium(0);

[0119]tetrakis(4,4'-dihydroxydibenzylideneacetone)dipalladium(0);

[0120]tris(4,4'-di(acetyloxy)dibenzylideneacetone)dipalladium(0);

[0121]bis(4,4'-di(acetyloxy)dibenzylideneacetone)palladium(b);

[0122]tetrakis(4,4'-di(acetyloxy)dibenzylideneacetone)dipalladium(0); and

[0123]tris(4,4'-di(acetyloxy)dibenzylideneacetone)palladium(0);

or salt thereof.

[0124]The complexes of the invention include the solvate adducts. The most
common solvents used to recrystallize Pd-dba complexes (and are thus most
likely to be incorporated as solvates in the crystal structure) are:
benzene, toluene, chloroform, dichloromethane, THF. In some embodiments,
the solvate is formed from dimethoxyethane, dioxane, and diethyl ether.
Other common solvents which may form adducts palladium complexes are
known in the art.

[0125]The palladium complexes may also form salts formed by the addition
of an acid or base to a compound disclosed herein. Generally, the
complexes of the invention with acidic groups (or groups that become
acidic upon hydrolysis or treatment with fluoride atom) can react with
bases. Acceptable salts, including mono- and bi-salts, include those
derived from alkali metal bases, alkaline earth metal bases, and other
useful bases. Acceptable salts, including mono- and bi- salts, include,
but are not limited to, those derived from organic and inorganic acids
such as, but not limited to, acetic, lactic, citric, cinnamic, tartaric,
succinic, fumaric, maleic, malonic, mandelic, malic, oxalic, propionic,
hydrochloric, hydrobromic, phosphoric, nitric, sulfuric, glycolic,
pyruvic, methanesulfonic, ethanesulfonic, toluenesulfonic, salicylic,
benzoic, and similarly known acceptable acids.

[0126]The complexes in this invention may contain one or more asymmetric
centers, which can thus give rise to optical isomers (enantiomers) and
diastereomers. While shown without respect to the stereochemistry in
Formula I, the present invention includes such optical isomers
(enantiomers) and diastereomers (geometric isomers); as well as the
racemic and resolved, enantiomerically pure R and S stereoisomers; as
well as other mixtures of the R and S stereoisomers and pharmaceutically
acceptable salts thereof.

[0127]One skilled in the art will also recognize that it is possible for
tautomers to exist for the complexes of the present invention. The
present invention includes all such tautomers even though not shown in
the formulas herein.

[0128]Complexes of the invention can also include all isotopes of atoms
occurring in the intermediates or final compounds. Isotopes include those
atoms having the same atomic number but different mass numbers. For
example, isotopes of hydrogen include tritium and deuterium.

[0129]At various places in the present specification, substituents of
compounds of the invention are disclosed in groups or in ranges. It is
specifically intended that the invention include each and every
individual subcombination of the members of such groups and ranges. For
example, the term "C1-6 alkyl" is specifically intended to
individually disclose methyl, ethyl, C3 alkyl, C4 alkyl,
C5 alkyl, and C6 alkyl.

[0130]It is further appreciated that certain features of the invention,
which are, for clarity, described in the context of separate embodiments,
can also be provided in combination in a single embodiment. Conversely,
various features of the invention which are, for brevity, described in
the context of a single embodiment, can also be provided separately or in
any suitable subcombination.

[0131]For compounds of the invention in which a variable appears more than
once, each variable can be a different moiety independently selected from
the group defining the variable. For example, where a structure is
described having two R groups that are simultaneously present on the same
compound; the two R groups can represent different moieties independently
selected from the group defined for R. In another example, when an
optionally multiple substituent is designated in the form:

##STR00008##

then it is understood that substituent R can occur p number of times on
the ring, and R can be a different moiety at each occurrence. Further, in
the above example, should the variable Q be defined to include hydrogens,
such as when Q is the to be CH2, NH, etc., any floating substituent
such as R in the above example, can replace a hydrogen of the Q variable
as well as a hydrogen in any other non-variable component of the ring.

[0132]The term "n-membered" where n is an integer typically describes the
number of ring-forming atoms in a moiety where the number of ring-forming
atoms is n. For example, piperidinyl is an example of a 6-membered
heterocycloalkyl ring and 1,2,3,4-tetrahydro-naphthalene is an example of
a 10-membered cycloalkyl group.

[0134]As used herein, the term "alkyl", employed alone or in combination
with other terms, refers to a saturated hydrocarbon group that may be
straight-chain or branched. In some embodiments, the alkyl group has 1 to
4, 2 to 4, 3 to 4, 3 to 6, 1 to 3 or 1 to 2 carbon atoms. Examples of
alkyl moieties include, but are not limited to, chemical groups such as
methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl,
sec-butyl; higher homologs such as 2-methyl-l-butyl, n-pentyl, 3-pentyl,
n-hexyl, 1,2,2-trimethylpropyl, n-heptyl, n-octyl, and the like.

[0135]As used herein, the term "amino" refers to a group of formula
--NH2.

[0136]As used herein, the term "alkylamino" refers to a group of formula
--NH(alkyl). In some embodiments, the alkyl group has 1 to 4, 2 to 4, 3
to 4, 3 to 6, 1 to 3 or 1 to 2 carbon atoms.

[0137]As used herein, the term "dialkylamino" refers to a group of formula
--N(alkyl)2. The prefix "C2-8" refers to the total number of
carbon atoms in the entire --N(alkyl)2 moiety, rather than the number in
one of the alkyl groups. In some embodiments, each alkyl group has 1 to
4, 2 to 4, 3 to 4, 3 to 6, 1 to 3 or 1 to 2 carbon atoms.

[0138]As used herein, the term "alkylene" refers to a divalent alkyl
linking group. Examples of alkylene groups include, but are not limited
to, methan-1,1-diyl, ethan-1,2-diyl, propan-1,3-diyl, propan-1,2-diyl,
butan-1,4-diyl, butan-1,3-diyl, butan-1,2-diyl, 2-methyl-propan-1,3-diyl,
and the like. In some embodiments, the alkylene group has 1 to 4, 2 to 4,
3 to 4, 3 to 6, 1 to 3, or 1 to 2 carbon atoms.

[0139]As used herein, "alkenyl", employed alone or in combination with
other terms, refers to an alkyl group having one or more double
carbon-carbon bonds. In some embodiments, the alkenyl moiety contains 2
to 4 carbon atoms.

[0140]As used herein, "alkynyl", employed alone or in combination with
other terms, refers to an alkyl group having one or more triple
carbon-carbon bonds. In some embodiments, the alkynyl moiety contains 2
to 4 carbon atoms.

[0141]As used herein, "non-terminal alkenyl", employed alone or in
combination with other terms, refers to an alkyl group having one or more
double carbon-carbon bonds, where the double bond is not in the terminal
position (opposite end from the linker) of the moiety (for example, an
alkenyl group having a double bond in the terminal position includes
--CH2--C═CH, and --CH2CH2--C═CH). In some
embodiments, the alkenyl moiety contains 2 to 4 carbon atoms.

[0142]As used herein, "non-terminal alkynyl", employed alone or in
combination with other terms, refers to an alkyl group having one or more
triple carbon-carbon bonds, where the triple bond is not in the terminal
position (opposite end from the linker) of the moiety. In some
embodiments, the alkynyl moiety contains 2 to 4 carbon atoms.

[0143]As used herein, the term "alkoxy", employed alone or in combination
with other terms, refers to an group of formula --O-alkyl. Example alkoxy
groups include methoxy, ethoxy, propoxy (e.g., n-propoxy and isopropoxy),
t-butoxy, and the like. In some embodiments, the alkoxy group has 1 to 4,
2 to 4, 3 to 4, 3 to 6, 1 to 3 or 1 to 2 carbon atoms.

[0144]As used herein, the term "alkyloxycarbonyl" refers to a group of
formula --C(O)O-(alkyl). In some embodiments, the alkyl group has 1 to 4,
2 to 4, 3 to 4, 3 to 6, 1 to 3 or 1 to 2 carbon atoms.

[0145]As used herein, the term "haloalkyloxycarbonyl" refers to a group of
formula --C(O)O-(haloalkyl). In some embodiments, the haloalkyl group has
1 to 4, 2 to 4, 3 to 4, 3 to 6, 1 to 3 or 1 to 2 0 carbon atoms.

[0146]As used herein, the term "carboxy" refers to a group of formula
--C(O)OH.

[0147]As used herein, the term "cycloalkyl", employed alone or in
combination with other terms, refers to a non-aromatic cyclic hydrocarbon
moiety, which may optionally contain one or more alkenylene or alkynylene
groups as part of the ring structure. Example cycloalkyl groups include
cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

[0148]As used herein, the term "cyano" refers to a group of formula --CN,
wherein the carbon and nitrogen atoms are bound together by a triple
bond.

[0149]As used herein, "haloalkoxy", employed alone or in combination with
other terms, refers to a group of formula --O-haloalkyl. In some
embodiments, the haloalkoxy group has 1 to 4, 2 to 4, 3 to 4, 3 to 6, 1
to 3 or 1 to 2 carbon atoms. In some embodiments, the haloalkoxy group
contains only fluorine atoms. An example haloalkoxy group is OCF3.

[0150]As used herein, the term "haloalkyl", employed alone or in
combination with other terms, refers to an alkyl group having from one
halogen atom to 2n+1 halogen atoms which may be the same or different,
where "n" is the number of carbon atoms in the alkyl group. In some
embodiments, the haloalkyl group has 1 to 4, 2 to 4, 3 to 4, 3 to 6, 1 to
3 or 1 to 2 carbon atoms. In some embodiments, the haloalkyl group
contains only fluorine atoms.

[0151]As used herein, the terms "halo" and "halogen", employed alone or in
combination with other terms, refer to fluoro, chloro, bromo, and iodo.

[0152]As used herein, the term "heteroaryl", "heteroaryl ring", or
"heteroaryl group", employed alone or in combination with other terms,
refers to a monocyclic aromatic hydrocarbon moiety, having one or more
heteroatom ring members selected from nitrogen, sulfur and oxygen. When
the heteroaryl group contains more than one heteroatom ring member, the
heteroatoms may be the same or different. Example heteroaryl groups
include, but are not limited to, pyrrolyl, azolyl, oxazolyl, thiazolyl,
imidazolyl, furyl, thienyl, or the like.

[0153]As used herein, the term "heterocycloalkyl", "heterocycloalkyl
ring", or "heterocycloalkyl group", employed alone or in combination with
other terms, refers to non-aromatic ring system, which may optionally
contain one or more alkenylene or alkynylene groups as part of the ring
structure, and which has at least one heteroatom ring member selected
from nitrogen, sulfur and oxygen. When the heterocycloalkyl groups
contains more than one heteroatom, the heteroatoms may be the same or
different. Heterocycloalkyl groups can include mono-ring systems. In some
embodiments, the heterocycloalkyl group has 5 to 6 ring-forming atoms, 5
to 7 ring-forming atoms, or about 3 to 8 ring forming atoms. The carbon
atoms or hetereoatoms in the ring(s) of the heterocycloalkyl group can be
oxidized to form a carbonyl, or sulfonyl group (or other oxidized
linkage) or a nitrogen atom can be quaternized.

[0154]As used herein, the term "hydroxyl" refers to a group of formula
--OH.

[0155]As used herein, the term "nitro" refers to a group of formula
--NO2.

[0156]As used herein, the term "quaternary salt of C2-8 dialkylamino"
refers to the quaternized salt of the dialkylamino group, wherein a third
C1-4 alkyl group is bound to the nitrogen atom forming a salt. Any
suitable counterion is appropriate, including, but not limited to a
halide ion. Processes for forming quaternary ammonium salts are
well-known in the art (e.g, the use of methyl iodide or other alkylating
agent).

[0157]As used herein, the term "alkylcarbonyloxy" refers to a group of
formula --OC(O)(alkyl). In some embodiments, the alkyl group has 1 to 4,
2 to 4, 3 to 4, 3 to 6, 1 to 3 or 1 to 2 carbon atoms.

[0158]As used herein, the term "haloalkylcarbonyloxy" refers to a group of
formula --OC(O)(haloalkyl). In some embodiments, the haloalkyl group has
1 to 4, 2 to 4, 3 to 4, 3 to 6, 1 to 3 or 1 to 2 carbon atoms.

[0159]As used herein, the term "tri(C1-4 alkyl)silyloxy" refers to a
group of formula --OSi(C1-4 alkyl)3. In some embodiments, the
alkyl group has 1 to 4, 2 to 4, 3 to 4, 3 to 6, 1 to 3 or 1 to 2 carbon
atoms.

[0160]As used herein, the term "tri(C1-4 haloalkyl)silyloxy" refers
to a group of formula --OSi(C1-4 haloalkyl)3. In some
embodiments, the haloalkyl group has 1 to 4, 2 to 4, 3 to 4, 3 to 6, 1 to
3 or 1 to 2 carbon atoms.

[0161]As used herein, the term "adjacent groups" means that the two "R"
substituents are on neighboring carbons of one of the phenyl rings in the
structure of Formula Ia.

[0162]In some embodiments, the present invention provides the product of
process comprising reacting palladium(II) with a ligand of Formula Ia, or
salt thereof, and sodium acetate in an alcohol solvent in the presence of
oxygen, wherein:

[0164]or two adjacent groups selected from R1, R2, R3,
R4, and R5, along with the carbons to which they are attached,
form a fused phenyl ring or a 5- or 6-membered heteroaryl ring, each of
which is optionally substituted by 1 to 2 independently selected Ra
groups;

[0165]or two adjacent groups selected from R6, R7, R8,
R9, and R10, along with the carbons to which they are attached,
form a fused phenyl ring or a 5- or 6-membered heteroaryl ring, each of
which is optionally substituted by 1 to 2 independently selected Rb
groups; and

[0169](2) if one of R1, R2, R3, R4, and R5 is
selected from C3-6 cycloalkyl, phenyl, a 5- or 6-heteroaryl ring,
and a 5- or 6-membered hetercycloalkyl ring; then: (a) the remaining
R1, R2, R3, R4, and R5 are not selected from
C3-6 cycloalkyl, phenyl, a 5- or 6-membered heteroaryl ring, and a
5- and 6-membered hetercycloalkyl ring; and (b) the remaining R1,
R2, R3, R4, and R5 adjacent groups, along with the
carbons to which they are attached, do not form a fused phenyl ring or a
5- or 6-membered heteroaryl ring, each of which is optionally substituted
by 1 to 2 Ra independently selected groups; and

[0170](3) if one of R6, R7, R8, R9, and R10 is
selected from C3-6 cycloalkyl, phenyl, a 5- or 6-membered heteroaryl
ring, or a 5- or 6-membered hetercycloalkyl ring; then (a) the remaining
R6, R7, R8, R9, and R10 groups are not selected
from C3-6 cycloalkyl, phenyl, a 5- or 6-membered heteroaryl ring,
and a 5- and 6-membered hetercycloalkyl ring; and (b) the remaining
R6, R7, R8, R9, and R10 adjacent groups, along
with the carbons to which they are attached, do not form a fused phenyl
ring or a 5- or 6-membered heteroaryl ring, each of which is optionally
substituted by 1 to 2 Rb independently selected groups; and

[0171](4) if two adjacent groups selected from R1, R2, R3,
R4, and R5, along with the carbons to which they are attached,
form a fused phenyl ring or a 5- or 6-membered heteroaryl ring, each of
which is optionally substituted by 1 to 2 Ra independently selected
groups; then: (a) the remaining R1, R2, R3, R4, and
R5 groups are not selected from C3-6 cycloalkyl, phenyl, a 5-
or 6-membered heteroaryl ring, and a 5- or 6-membered hetercycloalkyl
ring; and (b) the remaining R1, R2, R3, R4, and
R5 adjacent groups, along with the carbons to which they are
attached, do not form a fused phenyl ring or a 5- or 6-membered
heteroaryl ring, each of which is optionally substituted by 1 to 2
Ra independently selected groups; and

[0172](5) if two adjacent groups selected from R6, R7, R8,
R9, and R10, along with the carbons to which they are attached,
form a fused phenyl ring or a 5- or 6-membered heteroaryl ring, each of
which is optionally substituted by 1 to 2 Rb independently selected
groups; then: (a) the remaining R6, R7, R8, R9, and
R10 groups are not selected from C3-6 cycloalkyl, phenyl, a 5-
or 6-membered heteroaryl ring, and a 5- or 6-membered hetercycloalkyl
ring; and (b) the remaining R6, R7, R8, R9, and
R10 adjacent groups, along with the carbons to which they are
attached, do not form a fused phenyl ring or a 5- or 6-membered
heteroaryl ring, each of which is optionally substituted by 1 to 2
Rb independently selected groups.

[0173]In some embodiments, the temperature is about 40 to 50° C.

Processes and Reaction Mixtures

[0174]The present invention further provides process for preparing a
diaromatic compounds and polymerization processes. The polymerization
processes and processes for producing diaromatic compounds are Suzuki
polymerization and coupling reactions which are well-known in the art.
The processes utilizing the palladium complexes of the invention provide
improved yields and molecular weights in the polymers produced, due to
the palladium complexes used.

[0175]Accordingly, the present invention further provides a process for
preparing a diaromatic compound, comprising mixing a palladium complex of
the invention, an aromatic substrate having one group selected from
bromo, iodo, tosylate, benzenesulfonate, mesylate, triflate, and chloro,
an aromatic boronate having one group selected from boronic acid, boronic
ester, and borane, a base, a ligand, an organic solvent, and water and
reacting under conditions sufficient to form the diaromatic compound.

[0176]Accordingly, the present invention further provides a process for
preparing a diaromatic compound, comprising mixing a palladium complex of
the invention, or any of the embodiments herein, with a composition
comprising one or more materials selected from an aromatic substrate
having one group selected from bromo, iodo, tosylate, benzenesulfonate,
mesylate, triflate, and chloro, an aromatic boronate having one group
selected from boronic acid, boronic ester, and borane, a base, a ligand,
an organic solvent, and water; and after the mixing, adding the remaining
one or more materials and reacting under conditions sufficient to form a
diaromatic compound.

[0177]Further, in some embodiments, the present invention provides a
process for preparing a compound, comprising mixing a palladium complex
of the invention, an aromatic substrate or vinyl substrate, each having
one group selected from bromo, iodo, tosylate, benzenesulfonate,
mesylate, triflate, and chloro, an aromatic boronate, vinyl boronate, or
alkyl boronate, each having one group selected from boronic acid, boronic
ester, and borane, a base, a ligand, an organic solvent, and water and
reacting under conditions sufficient to form the diaromatic compound.

[0178]As used herein, the term "aromatic substrate", as used in this
context, refers to any aromatic moiety which can be used for a Suzuki
coupling reaction, having an aryl or heteroaryl moiety, wherein the
aromatic moiety has one group selected from bromo, iodo, tosylate,
benzenesulfonate, mesylate, triflate, and chloro, which is attached to
the aryl or heteroaryl moiety, and which can be optionally substituted.
Many aromatic substrates can be used (see e.g., Suzuki, A., J. Organomet.
Chem. 2002, 653, 83; Miyaura, N., Top. Curr. Chem. 2002, 219, 12; Suzuki,
A., in Handbook of Organopalladium Chemistry for Organic Synthesis,
Negishi, E., Ed.; John Wiley & Sons, Inc.: Hoboken, N.J., 2002; Vol. 1,
p. 249).

[0179]As used herein, the term "aromatic boronate", as used in this
context, refers to any aromatic moiety which can be used for a Suzuki
coupling reaction, having an aryl or heteroaryl moiety, wherein the
aromatic moiety has one group selected from boronic acid, boronic ester,
and borane, which is attached to the aryl or heteroaryl moiety, and which
can be optionally substituted. Many aromatic boronates can be used (see
e.g., Suzuki, A., J. Organomet. Chem. 2002, 653, 83; Miyaura, N., Top.
Curr. Chem. 2002, 219, 12; Suzuki, A., in Handbook of Organopalladium
Chemistry for Organic Synthesis, Negishi, E., Ed.; John Wiley & Sons,
Inc.: Hoboken, N.J., 2002; Vol. 1, p. 249).

[0180]As used herein, the term "vinyl boronate", as used in this context,
refers to an alkenyl moiety which may be optionally substituted, which
can be used for a Suzuki coupling reaction, wherein the alkenyl moiety
has a group attached to the double bond, wherein the group is selected
from boronic acid, boronic ester, and borane, which can be optionally
substituted.

[0181]As used herein, the term "vinyl substrate", as used in this context,
refers to an alkenyl moiety which may be optionally substituted, which
can be used for a Suzuki coupling reaction, wherein the alkenyl moiety
has a group attached to the double bond, wherein the group is selected
from bromo, iodo, tosylate, benzenesulfonate, mesylate, triflate, and
chloro, which can be optionally substituted.

[0182]As used herein, the term "alkyl boronate", as used in this context,
refers to an alkyl moiety which may be optionally substituted, which can
be used for a Suzuki coupling reaction, wherein the alkyl moiety is
substituted by a group selected from boronic acid, boronic ester, and
borane, which can be optionally substituted.

[0183]As used herein, the term "diaromatic compound" refers to the product
of the Suzuki coupling of the aromatic boronate and the aromatic
substrate.

[0184]As used herein, the term "aryl moiety", used in this context, refers
to a monocyclic or polycyclic (e.g., having 2, 3 or 4 fused or covalently
linked rings) aromatic hydrocarbon moiety, such as, but not limited to,
phenyl, 1-naphthyl, 2-naphthyl, anthracenyl, phenanthrenyl, and the like,
which may be optionally substituted. In some embodiments, aryl groups
have from 6 to 20 carbon atoms, about 6 to 10 carbon atoms, or about 6 to
8 carbons atoms.

[0185]As used herein, the term "heteroaryl moiety", used in this context,
refers to a monocyclic or polycyclic (e.g., having 2, 3 or 4 fused or
covalently linked rings) aromatic hydrocarbon moiety, having one or more
heteroatom ring members selected from nitrogen, sulfur and oxygen. When
the heteroaryl group contains more than one heteroatom ring member, the
heteroatoms may be the same or different. Example heteroaryl groups
include, but are not limited to, pyrrolyl, azolyl, oxazolyl, thiazolyl,
imidazolyl, furyl, thienyl, quinolinyl, isoquinolinyl, indolyl,
benzothienyl, benzofuranyl, benzisoxazolyl, imidazo[1,2-b]thiazolyl or
the like. In some embodiments, the heteroaryl group has 5 to 10 carbon
atoms.

[0186]While not wishing to be bound by any theory, in some embodiments,
the processes provide diaromtic compounds in a higher yield and/or purity
because of the better delivery of the palladium(0) metal into the
catalytic cycle, provided by the palladium complexes of the invention. In
some embodiments, the processes provide diaromtic compounds starting from
aromatic chlorides as the aromatic substrate. Aromatic chlorides can be
obtained at lower cost than the other aromatic substrates having from
bromo, iodo, tosylate, benzenesulfonate, mesylate, and triflate groups.

[0188]As used herein, the term "composition" refers to either a mixture of
materials or a single material.

[0189]In some embodiments, the group on the aromatic substrate is selected
from bromo, iodo, tosylate, benzenesulfonate, mesylate, triflate, and
chloro. In some embodiments, the group on the aromatic substrate is
selected from bromo, iodo, tosylate, benzenesulfonate, mesylate, and
triflate. In some embodiments, the group on the aromatic substrate is
selected from bromo, iodo, and chloro. In some embodiments, the group on
the aromatic substrate is selected from bromo and iodo.

[0190]In some embodiments, the aromatic substrate has an aryl moiety
substituted by one group selected from bromo, iodo, tosylate,
benzenesulfonate, mesylate, triflate, and chloro; and the aromatic
boronate has an aryl moiety substituted by one group selected from
boronic acid, boronic ester, and borane. In some embodiments, the
aromatic substrate has a phenyl ring substituted by one group selected
from bromo, iodo, tosylate, benzenesulfonate, mesylate, triflate, and
chloro; and the aromatic boronate has a phenyl ring substituted by one
group selected from boronic acid, boronic ester, and borane. In some
embodiments, the aromatic substrate has an aryl moiety substituted by one
group selected from bromo, iodo, and chloro; and the aromatic boronate
having an aryl moiety substituted by one group selected from boronic
acid, and boronic ester. In some embodiments, the aromatic substrate has
a phenyl ring substituted by one group selected from bromo, iodo, and
chloro; and the aromatic boronate has a phenyl ring substituted by one
group selected from boronic acid and boronic ester. In some embodiments,
the aromatic substrate has an aryl moiety substituted by one group
selected from bromo and iodo; and the aromatic boronate having an aryl
moiety substituted by one group selected from boronic acid, and boronic
ester. In some embodiments, the aromatic substrate has a phenyl ring
substituted by one group selected from bromo and iodo; and the aromatic
boronate has a phenyl ring substituted by one group selected from boronic
acid and boronic ester.

[0192]Suitable organic solvents include, but are not limited to,
dichloromethane, chloroform, toluene, benzene, THF, dimethoxyethane,
dioxane, dimethylacetamide, dimethylsulfoxide, and dimethylformamide.
Other other solvents for Suzuki coupling are known in the art.

[0193]In some embodiments, the molar ratio of ligand to palladium metal is
from 1:1 to 2:1.

[0194]In some embodiments, the conditions sufficient to form a diaromatic
compound comprise heating to a temperature of from about 30 to about
120° C. In some embodiments, the conditions sufficient to form a
diaromatic compound comprise heating to a temperature of from about 30 to
about 80° C. In some embodiments, the conditions sufficient to
form a diaromatic compound comprise heating to a temperature of from
about 30 to about 120° C. for about 0.5 hours to about 48 hours.
In some embodiments, the conditions sufficient to form a diaromatic
compound comprise heating to a temperature of from about 30 to about
80° C. for about 0.5 hours to about 24 hours. In some embodiments,
the conditions sufficient to form a diaromatic compound comprise heating
to a temperature of about 50° C. for about 24 hours to about 100
hours, or about 72 hours.

[0195]In some embodiments, the base used in the reaction may be an
inorganic base such as an alkaline earth carbonate or bicarbonate or an
organic base, such as those organic bases disclosed in WO00/53656,
including alkyl ammonium hydroxides, alkyl ammonium carbonates, alkyl
ammonium biscarbonates, alkylammonium borates,
1,5-diazabicyclo[4.3.0]non-5-ene (DBN),
1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,4-diazabicyclo[2.2.2]octane
(DABCO), dimethylaminopyridine (DMAP), pyridine, trialkylamines and
alkylammonium fluorides such as tetraalkylammonium fluorides. In some
embodiments, the base is a tetraalkyl ammonium hydroxide such as
tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide or
tetra-n-propyl ammonium hydroxide. In some embodiments, the base is
selected from an alkali carbonate, an alkali bicarbonate, an alkaline
earth carbonate, an alkaline earth bicarbonate, an organic base, an
alkali phosphate, an alkali fluoride, an alkaline earth fluoride, and an
alkaline earth phosphate.

[0196]Generally, in some embodiments, enough base is used so as to
deprotonate the base labile groups or acidic groups on the palladium
complex, such as the hydroxyl groups, or to facilitate the hydroxylsis of
the protected groups on the complex such as the C1-4
alkylcarbonyloxy groups. Additionally, in some embodiments, the base is
usually added in a quantity sufficient to convert the boron derivative
functional groups into --B(OH)3 or --BF3 anionic groups
depending on the particular base selected.

[0197]Any of the aromatic substrates, aromatic diboronates, ligands,
solvents, bases, conditions, and palladium complexes described herein can
combined in any suitable combination to perform the coupling processes of
the invention.

[0198]The present invention further provides a polymerization process
comprising mixing a palladium complex of the invention, or any embodiment
described herein, with an aromatic substrate having two groups
independently selected from bromo, iodo, tosylate, benzenesulfonate,
mesylate, triflate, and chloro, an aromatic diboronate having two groups
independently selected from boronic acid, boronic ester, and borane, a
base, a ligand, a organic solvent and water; and reacting under
conditions sufficient to form a polymer.

[0199]The present invention further provides a polymerization process
comprising mixing a palladium complex of the invention, or any embodiment
described herein, with a composition comprising one or more materials
selected from an aromatic substrate having two groups independently
selected from bromo, iodo, tosylate, benzenesulfonate, mesylate,
triflate, and chloro, an aromatic diboronate having two groups
independently selected from boronic acid, boronic ester, and borane, a
base, a ligand, a organic solvent and water; and

[0200]after the mixing, adding the remaining one or more materials and
reacting under conditions sufficient to form a polymer.

[0201]In some embodiments, each group on the aromatic substrate is
independently selected from bromo, iodo, tosylate, benzenesulfonate,
mesylate, triflate, and chloro. In some embodiments, each group on the
aromatic substrate is independently selected from bromo, iodo, tosylate,
benzenesulfonate, mesylate, and triflate. In some embodiments, each group
on the aromatic substrate is independently selected from bromo, iodo, and
chloro. In some embodiments, each group on the aromatic substrate is
independently selected from bromo and iodo.

[0202]In some embodiments, the aromatic substrate has an aryl moiety
substituted by two groups independently selected from bromo, iodo,
tosylate, benzenesulfonate, mesylate, triflate, and chloro; and the
aromatic diboronate has an aryl moiety substituted by two groups
independently selected from boronic acid, boronic ester, and borane. In
some embodiments, the aromatic substrate has a phenyl ring substituted by
two groups independently selected from bromo, iodo, tosylate,
benzenesulfonate, mesylate, triflate, and chloro; and the aromatic
diboronate has a phenyl ring substituted by two groups independently
selected from boronic acid, boronic ester, and borane group. In some
embodiments, the aromatic substrate has an aryl moiety substituted by two
groups independently selected from bromo, iodo, and chloro; and the
aromatic diboronate has an aryl moiety substituted by two groups
independently selected from boronic acid and boronic ester. In some
embodiments, the aromatic substrate has a phenyl ring substituted by two
groups independently selected from bromo, iodo, and chloro; and the
aromatic diboronate has a phenyl ring substituted by two groups
independently selected from boronic acid and boronic ester. In some
embodiments, the aromatic substrate has an aryl moiety substituted by two
groups independently selected from bromo and iodo; and the aromatic
diboronate has an aryl moiety substituted by two groups independently
selected from boronic acid and boronic ester. In some embodiments, the
aromatic substrate has a phenyl ring substituted by two groups
independently selected from bromo and iodo; and the aromatic diboronate
has a phenyl ring substituted by two groups independently selected from
boronic acid and boronic ester.

[0203]As used herein, the term "polymer" refers to the product of the
Suzuki polymerization of the aromatic substrate and the aromatic
diboronate. The polymers may be conjugated polymers. The term conjugated
refers to either a fully conjugated polymer i.e. a polymer which is
conjugated along the full length of its chain, or a partially conjugated
polymer i.e. a polymer which contains conjugated segments together with
non-conjugated segments. The polymers are formed by coupling together two
monomers: at least one "aromatic substrate" and at least one "aromatic
diboronate".

[0204]As used herein, the term "aromatic substrate", as used in this
context, refers to any aromatic moiety which can be used for a Suzuki
polymerization, having an aryl or heteroaryl moiety, wherein the aromatic
moiety has two groups selected from bromo, iodo, tosylate,
benzenesulfonate, mesylate, triflate, and chloro, which is attached to
the aryl or heteroaryl moiety, and which can be optionally substituted.
Many aromatic substrates can be used (see e.g., Schluter, A. D., J.
Polym. Sci., Polym. Chem. Ed. 2001, 39, 1533; and Schluter, A.-D.; Bo,
Z., in Handbook of Organopalladium Chemistry for Organic Synthesis,
Negishi, E., Ed.; John Wiley & Sons, Inc.: Hoboken, N.J., 2002; Vol. 1, p
825).

[0205]As used herein, the term "aromatic diboronate", as used in this
context, refers to any aromatic moiety which can be used for a Suzuki
polymerization, having an aryl or heteroaryl moiety, wherein the aromatic
moiety has two groups selected from boronic acid, boronic ester, and
borane, which is attached to the aryl or heteroaryl moiety, and which can
be optionally substituted. Many aromatic diboronates can be used (see
e.g., Schluter, A. D., J. Polym. Sci., Polym. Chem. Ed. 2001, 39, 1533;
and Schluter, A.-D.; Bo, Z., in Handbook of Organopalladium Chemistry for
Organic Synthesis, Negishi, E., Ed.; John Wiley & Sons, Inc.: Hoboken,
N.J., 2002; Vol. 1, p 825).

[0206]As used herein, the term "aryl moiety", used in this context, refers
to a monocyclic or polycyclic (e.g., having 2, 3 or 4 fused or covalently
linked rings) aromatic hydrocarbon moiety, such as, but not limited to,
phenyl, 1-naphthyl, 2-naphthyl, anthracenyl, phenanthrenyl, and the like,
which may be optionally substituted. In some embodiments, aryl groups
have from 6 to 20 carbon atoms, about 6 to 10 carbon atoms, or about 6 to
8 carbons atoms.

[0207]As used herein, the term "heteroaryl moiety", used in this context,
refers to a monocyclic or polycyclic (e.g., having 2, 3 or 4 fused or
covalently linked rings) aromatic hydrocarbon moiety, having one or more
heteroatom ring members selected from nitrogen, sulfur and oxygen. When
the heteroaryl group contains more than one heteroatom ring member, the
heteroatoms may be the same or different. Example heteroaryl groups
include, but are not limited to, pyrrolyl, azolyl, oxazolyl, thiazolyl,
imidazolyl, furyl, thienyl, quinolinyl, isoquinolinyl, indolyl,
benzothienyl, benzofuranyl, benzisoxazolyl, imidazo[1,2-b]thiazolyl or
the like. In some embodiments, the heteroaryl group has 5 to 10 carbon
atoms.

[0208]With respect to the boronic acid, boronic ester, and borane, the
boronic acid group is represented by --B(OH)2; the boronic ester
group is preferably --B(ORx)(ORy) or --B(ORwO) and the
borane group is preferably --BRcRd, wherein Rx is a
substituted or non-substituted C1-C6 alkyl group and Ry is
H or a substituted or non-substituted C1-C6 alkyl group;
Rc and Rd are each independently substituted or nonsubstituted
C1-C6 alkyl groups, and Rw is a substituted or
non-substituted divalent hydrocarbon radical resulting in a 5 or 6
membered ester ring. Examples of suitable groups as Rw include
substituted or non-substituted C2 or C3 alkylene groups, or
substituted or non-substituted ortho-or metaphenylene groups. Suitable
boronic ester groups include, for example, the products of esterification
of the corresponding boronic acid group with monovalent C1-C6
alcohols, ethane diols such as pinacol, propane diols or ortho aromatic
diols such as 1,2-dihydroxybenzene.

[0209]Examples of suitable types of aromatic substrates and aromatic
diboronates include, but are not limited to, fluorenes, quinoxalines,
benzothiazoles, triarylamines, phenylenes, thiophenes, naphthylenes and
stilbenes. Each aromatic group within the monomer may be substituted or
unsubstituted. In some embodiments, the aromatic substrates and aromatic
diboronates are those aromatic monomers moieties comprising fused
carbocyclic rings, comprising heterocyclic rings or comprising
triarylamines including fluorenes, benzothiadiazoles, triarylamines,
thiophenes and quinoxalines. In some embodiments, the aromatic substrates
and aromatic diboronates include fluorenes and arylamines such as
9,9-dioctylfluorene (F8), benzothiadiazole (BT),
(1,4-phenylene-((4-secbutylphenyl)imino)-1,4-phenylene) (TFB),
(2,7-(9,9-di-n-octylfluorene)-3,6-benzothiadiazole) (F8BT). In some
embodiments, the aromatic substrates and aromatic diboronates include a
pre-formed oligomeric or polymeric chain comprising several smaller units
with the necessary functional groups provided at the desired positions on
the chain. In some embodiments, the aromatic substrates and aromatic
diboronates are those shown below, wherein X1 and X2 are
reactive boron derivative groups or reactive halides.

[0211]Monomers particularly useful in the present invention include those
which may be polymerised to form a semiconductive polymer such as a
semiconductive conjugated polymer for use in an optical device such as an
electroluminescent device, suitable monomers include fluorenes,
benzothiazoles, triarylamines, thiophenes and quinoxalines. Such polymers
may be used in an emissive layer or as a hole transport or electron
transport polymer. Luminescent polymers are particularly useful in such
devices. The conjugated polymer may be fully or partially conjugated,
perhaps containing conjugated segments and may be a homopolymer, a
copolymer or an oligomer, and may be a linear or a branched chain polymer
such as a dendrimer.

[0212]The monomers each have the appropriate functional groups for the
Suzuki reaction. In one arrangement, a first reactive dihalide aromatic
substrate is polymerised with a second aromatic diboronate having two
boron derivative functional groups. In this arrangement the first and the
second monomers may be the same or different. Where the monomers are the
same, a homopolymer is produced. Where the monomers are different, a
copolymer is produced.

[0213]In a second arrangement, a monomer having a boron derivative
functional group and a reactive halide functional group is polymerised to
form a homopolymer. It is also possible to form copolymers from this
second arrangement simply by polymerising together two or more different
types of monomer each containing both functionalities.

[0215]Suitable organic solvents include, but are not limited to,
dichloromethane, chloroform, toluene, benzene, THF, dimethoxyethane,
dioxane, dimethylacetamide, dimethylsulfoxide, and dimethylformamide.
Other other solvents for Suzuki polymerizations are known in the art.

[0216]In some embodiments, the the molar ratio of ligand to palladium
metal is from 1:1 to 2:1.

[0217]For polymerizations, it is critical to match the stoichiometery of
the aromatic substrate and the aromatic diboronate as closely as possible
in order to maximize the molecular weight of the polymer, which is made
via a step polymerization. The polymerization processes can be carried
out using typical Suzuki reaction conditions, but using the palladium
complexes of the invention as the palladium source (for a review, see
Schluter, A. D., J. Polym. Sci., Polym. Chem. Ed. 2001, 39, 1533; and
Schluter, A.-D.; Bo, Z., in Handbook of Organopalladium Chemistry for
Organic Synthesis, Negishi, E., Ed.; John Wiley & Sons, Inc.: Hoboken,
N.J., 2002; Vol, 1, p 825).

[0218]In some embodiments, the conditions sufficient to form a polymer
comprise heating to a temperature of from about 30 to about 120°
C. In some embodiments, the conditions sufficient to form a polymer
comprise heating to a temperature of from about 30 to about 80° C.
In some embodiments, the conditions sufficient to form a polymer comprise
heating to a temperature of about 30 to about 120° C. for about 8
hours to 170 hours. In some embodiments, the conditions sufficient to
form a polymer comprise heating to a temperature of about 30 to about
80° C. for about 8 hours to 48 hours.

[0219]In some embodiments, the base used in the reaction may be an
inorganic base such as an alkaline earth carbonate or bicarbonate or an
organic base, such as those organic bases disclosed in WO00/53656,
including alkyl ammonium hydroxides, alkyl ammonium carbonates, alkyl
ammonium biscarbonates, alkylammonium borates,
1,5-diazabicyclo[4.3.0]non-5-ene (DBN),
1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,4-diazabicyclo[2.2.2]octane
(DABCO), dimethylaminopyridine (DMAP), pyridine, trialkylamines and
alkylammonium fluorides such as tetraalkylammonium fluorides. In some
embodiments, the base is a tetraalkyl ammonium hydroxide such as
tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide or
tetra-n-propyl ammonium hydroxide. In some embodiments, the base is
selected from an alkali carbonate, an alkali bicarbonate, an alkaline
earth carbonate, an alkaline earth bicarbonate, an organic base, an
alkali phosphate, an alkali fluoride, an alkaline earth fluoride, and an
alkaline earth phosphate.

[0220]Generally, in some embodiments, enough base is used so as to
deprotonate the base labile groups on the palladium complex, such as the
hydroxyl groups, or to facilitate the hydroxylsis of the protected groups
on the complex such as the C1-4 alkylcarbonyloxy groups.
Additionally, in some embodiments, the base is usually added in a
quantity sufficient to convert the boron derivative functional groups
into --B(OH)3 or --BF3 anionic groups depending on the
particular base selected.

[0221]Any of the aromatic substrates, aromatic diboronates, ligands,
solvents, bases, conditions, and palladium complexes described herein can
combined in any suitable combination to perform the polymerization
processes of the invention.

[0222]Polymers prepared according to the present invention may be used in
optoelectronic devices such as electroluminescent devices and
photovoltaic devices. An electroluminescent device typically comprises,
on a suitable substrate, an anode, a cathode and a layer of
light-emitting material positioned between the anode and the cathode.
Electroluminescent devices may further comprise charge transport layers
and/or charge injecting layers positioned between the light-emitting
material and the anode or cathode as appropriate. In electroluminescent
devices of the present invention the high molecular weight polymers of
the present invention may be present either as the light-emitting layer
or as charge transporting or charge injecting layers or alternatively as
charge transporting components in a blend with a light emitting material
or as light emitting components in a blend with a charge transporting
material. The thickness of the emitting layer can be in the range 10
nm-300 nm, preferably 50 nm-200 nm.

[0223]In some embodiments, the anode of the device preferably comprises a
material of high work function deposited on a substrate. Preferably the
material has a work function greater than 4.3 eV, examples of such
materials include indium-tin oxide (ITO), tin oxide (TO), aluminum or
indium doped zinc oxide, magnesium-indium oxide, cadmium tin-oxide and
metals such as Au, Ag, Ni, Pd and Pt. Suitable substrates include glass
and plastics, the substrate may be rigid or flexible, transparent or
opaque. The material of high work function is suitably deposited on the
substrate to form a film of 50 nm to 200 nm, preferably the film has a
sheet resistance of 10-100 Ohm/square, more preferably less than 30
Ohm/square.

[0224]In some embodiments, the cathode of the device is preferably a
material of low work function, preferably of work function less than 3.5
eV. Examples of such materials include Li, Na, K, Rb, Be, Mg, Ca, Sr, Ba,
Yb, Sm and Al, the cathode may comprise an alloy of such metals or an
alloy of such metals in combination with other metals, for example the
alloys MgAg and LiAl. The cathode preferably comprises multiple layers,
for example Ca/Al or LiAVAI, The device may further comprise a layer of
dielectric material between the cathode and the emitting layer, such as
is disclosed in WO 97/42666. In particular it is preferred to use an
alkali or alkaline earth metal fluoride as a dielectric layer between the
cathode and the emitting material. In some embodiments, the cathode
comprises LiF/Ca/AI, with a layer of LiF of thickness from 1 to 10 nm, a
layer of Ca of thickness 1 to 25 nm and a layer of Al of thickness 10 to
500 nm.

[0225]Where the electroluminescent device comprises further charge
injecting or charge transporting materials, these further materials may
be present as separate layers or in blend with the light emitting
material. Examples of suitable charge transporting materials include
polystyrene sulfonic acid doped polyethylene dioxythiophene (PEDOT-PSS),
polyaniline with anionic dopants such as polymeric anionic dopants, and
triarylamines, including polymeric triarylamines such as
poly(2,7-(9,9-ni-n-octylfluorene)-(1,4-phenylene-(4-imino(benzoic
acid))-1,4-phenylene-(4-imino(benzoic acid))-1,4-phenylene)) BFA. The
charge transport or charge injecting layers suitably have a thickness in
the range 10 nm to 200 nm, preferably 1 nm to 50 nm.

[0226]In some embodiments, the structure of an electroluminescent devices
comprises a glass substrate, an ITO anode, a charge transporting layer of
PEDOT-PSS, a layer of light-emitting material, a thin layer of LiF and a
cathode comprising a layer of calcium and a layer of aluminum. In some
embodiments, the polymers prepared according to the present invention
could also be suitably used in photovoltaic devices such as those
disclosed in WO96/16449.

[0227]The present invention further provides a mixture comprising an
aromatic substrate having one group selected from bromo, iodo, tosylate,
benzenesulfonate, mesylate, triflate, and chloro, an aromatic boronate
having one group selected from boronic acid, boronic ester, and borane; a
base, water, and a palladium complex of the invention or any of the
embodiments described herein. Any of the aromatic substrates, aromatic
boronates, ligands, solvents, bases, and palladium complexes described
herein can combined in any suitable combination to form the mixtures of
the invention. This mixture is prepared during the Suzuki coupling
processes of the invention. In some embodiments, the mixture further
comprises an organic solvent.

[0228]The present invention further provides a mixture comprising an
aromatic substrate having two groups selected from bromo, iodo, tosylate,
benzenesulfonate, mesylate, triflate, and chloro, an aromatic boronate
having one group selected from boronic acid, boronic ester, and borane; a
base, water, and a palladium complex of the invention or any of the
embodiments described herein. Any of the aromatic substrates, aromatic
diboronates, ligands, solvents, bases, and palladium complexes described
herein can combined in any suitable combination to form the mixtures of
the invention. This mixture is prepared during the Suzuki polymerization
processes of the invention. In some embodiments, the mixture further
comprises an organic solvent.

[0229]The present invention further provides a mixture comprising an
aromatic substrate having one group selected from bromo, iodo, tosylate,
benzenesulfonate, mesylate, triflate, and chloro, an aromatic boronate
having one group selected from boronic acid, boronic ester, and borane, a
base, water, and a ligand of Formula la, or salt thereof:

[0231]or two adjacent groups selected from R1, R2, R3,
R4, and R5, along with the carbons to which they are attached,
form a fused phenyl ring or a 5- or 6-membered heteroaryl ring, each of
which is optionally substituted by 1 to 2 Ra independently selected
groups;

[0232]or two adjacent groups selected from R6, R7, R8,
R9, and R10, along with the carbons to which they are attached,
form a fused phenyl ring or a 5- or 6-membered heteroaryl ring, each of
which is optionally substituted by 1 to 2 Rb independently selected
groups;

[0234](1) at least one of R1, R2, R3, R4, R5,
R6, R7, R8, R9, and R10 is independently
selected from hydroxyl, carboxy, di(C1-4 alkyl)amino,
HO--S(O)2--, HO--S(O)--, (HO)2P(O)--, and a quaternary salt of
C2-8 dialkylamino; wherein the C1-4 alkylene is substituted by
a moiety selected from carboxy, HO--S(O)2--, HO--S(O)--,
(HO)2P(O)--, and a quaternary salt of C2-8 dialkylamino;

[0235](2) if one of R1, R2, R3, R4, and R5 is
selected from C3-6 cycloalkyl, phenyl, a 5- or 6-membered heteroaryl
ring, and a 5- or 6-membered hetercycloalkyl ring; then: (a) the
remaining R1, R2, R3, R4, and R5 are not
selected from C3-6 cycloalkyl, phenyl, a 5- or 6-membered heteroaryl
ring, and a 5- and 6-membered hetercycloalkyl ring; and (b) the remaining
R1, R2, R3, R4, and R5 adjacent groups, along
with the carbons to which they are attached, do not form a fused phenyl
ring or a 5- or 6-membered heteroaryl ring, each of which is optionally
substituted by 1 to 2 Ra independently selected groups; and

[0236](3) if one of R6, R7, R5, R9, and R10 is
selected from C3-6 cycloalkyl, phenyl, a 5- or 6-membered heteroaryl
ring, or a 5- or 6-membered hetercycloalkyl ring; then (a) the remaining
R6, R7, R8, R9, and R10 groups are not selected
from C3-6 cycloalkyl, phenyl, a 5- or 6-membered heteroaryl ring,
and a 5- and 6-membered hetercycloalkyl ring; and (b) the remaining
R6, R7, R8, R9, and R10 adjacent groups, along
with the carbons to which they are attached, do not form a fused phenyl
ring or a 5- or 6-membered heteroaryl ring, each of which is optionally
substituted by 1 to 2 Rb independently selected groups; and

[0237](4) if two adjacent groups selected from R1, R2, R3,
R4, and R5, along with the carbons to which they are attached,
form a fused phenyl ring or a 5- or 6-membered heteroaryl ring, each of
which is optionally substituted by 1 to 2 Ra independently selected
groups; then: (a) the remaining R1, R2, R3, R4, and
R5 groups are not selected from C3-6 cycloalkyl, phenyl, a 5-
or 6-membered heteroaryl ring, and a 5- or 6-membered hetercycloalkyl
ring; and (b) the remaining R1, R2, R3, R4, and
R5 adjacent groups, along with the carbons to which they are
attached, do not form a fused phenyl ring or a 5- or 6-membered
heteroaryl ring, each of which is optionally substituted by 1 to 2
Ra independently selected groups; and

[0238](5) if two adjacent groups selected from R6, R7, R8,
R9, and R10, along with the carbons to which they are attached,
form a fused phenyl ring or a 5- or 6-membered heteroaryl ring, each of
which is optionally substituted by 1 to 2 Rb independently selected
groups; then: (a) the remaining R6, R7, R8, R9, and
R10 groups are not selected from C3-6 cycloalkyl, phenyl, a 5-
or 6-membered heteroaryl ring, and a 5- or 6-membered hetercycloalkyl
ring; and (b) the remaining R6, R7, R8, R9, and
R10 adjacent groups, along with the carbons to which they are
attached, do not form a fused phenyl ring or a 5- or 6-membered
heteroaryl ring, each of which is optionally substituted by 1 to 2
Rb independently selected groups.

[0239]The ligand is formed after hydrolysis of any hydrolyzable groups for
R1, R2, R3, R4, R5, R6, R7, R8,
R9, and R10, such as C1-4 alkylcarbonyloxy, C1-4
haloalkylcarbonyloxy, C1-4 alkyloxycarbonyl, C1-4
haloalkyloxycarbonyl, tri(C1-4 alkyl)silyloxy, or tri(C1-4
haloalkyl)silyloxy; or C1-4 alkylene substituted by a moiety
selected from C1-4 alkylcarbonyloxy, C1-4 haloalkylcarbonyloxy,
C1-4 alkyloxycarbonyl, and C1-4 haloalkyloxycarbonyl. This
mixture forms during the Suzuki coupling processes of the invention. In
some embodiments, the mixture further comprises an organic solvent.

[0240]The present invention further provides a mixture comprising an
aromatic substrate having two groups selected from bromo, iodo, tosylate,
benzenesulfonate, mesylate, triflate, and chloro, an aromatic diboronate
having two groups selected from boronic acid, boronic ester, and borane,
a base, water, and a ligand of Formula Ia:

[0242]or two adjacent groups selected from R1, R2, R3,
R4, and R5, along with the carbons to which they are attached,
form a fused phenyl ring or a 5- or 6-membered heteroaryl ring, each of
which is optionally substituted by 1 to 2 Ra independently selected
groups;

[0243]or two adjacent groups selected from R6, R7, R8,
R9, and R10, along with the carbons to which they are attached,
form a fused phenyl ring or a 5- or 6-membered heteroaryl ring, each of
which is optionally substituted by 1 to 2 Rb independently selected
groups;

[0245](1) at least one of R1, R2, R3, R4, R5,
R6, R7, R8, R9, and R10 is independently
selected from hydroxyl, carboxy, di(C1-4 alkyl)amino,
HO--S(O)2--, HO--S(O)--, (HO)2P(O)--, and a quaternary salt of
C2-8 dialkylamino; wherein the C1-4 alkylene is substituted by
a moiety selected from carboxy, HO--S(O)2--, HO--S(O)--,
(HO)2P(O)--, and a quaternary salt of C2-8 dialkylamino;

[0246](2) if one of R1, R2, R3, R4, and R5 is
selected from C3-6 cycloalkyl, phenyl, a 5- or 6-membered heteroaryl
ring, and a 5- or 6-membered hetercycloalkyl ring; then: (a) the
remaining R1, R2, R3, R4, and R5 are not
selected from C3-6 cycloalkyl, phenyl, a 5- or 6-membered heteroaryl
ring, and a 5- and 6-membered hetercycloalkyl ring; and (b) the remaining
R1, R2, R3, R4, and R5 adjacent groups, along
with the carbons to which they are attached, do not form a fused phenyl
ring or a 5- or 6-membered heteroaryl ring, each of which is optionally
substituted by 1 to 2 Ra independently selected groups; and

[0247](3) if one of R6, R7, R8, R9, and R10 is
selected from C3-6 cycloalkyl, phenyl, a 5- or 6-membered heteroaryl
ring, or a 5- or 6-membered hetercycloalkyl ring; then (a) the remaining
R6, R7, R8, R9, and R10 groups are not selected
from C3-6 cycloalkyl, phenyl, a 5- or 6-membered heteroaryl ring,
and a 5- and 6-membered hetercycloalkyl ring; and (b) the remaining
R6, R7, R8, R9, and R10 adjacent groups, along
with the carbons to which they are attached, do not form a fused phenyl
ring or a 5- or 6-membered heteroaryl ring, each of which is optionally
substituted by 1 to 2 Rb independently selected groups; and

[0248](4) if two adjacent groups selected from R1, R2, R3,
R4, and R5, along with the carbons to which they are attached,
form a fused phenyl ring or a 5- or 6-membered heteroaryl ring, each of
which is optionally substituted by 1 to 2 Ra independently selected
groups; then: (a) the remaining R1, R2, R3, R4, and
R5 groups are not selected from C3-6 cycloalkyl, phenyl, a 5-
or 6-membered heteroaryl ring, and a 5- or 6-membered hetercycloalkyl
ring; and (b) the remaining R1, R2, R3, R4, and
R5 adjacent groups, along with the carbons to which they are
attached, do not form a fused phenyl ring or a 5- or 6-membered
heteroaryl ring, each of which is optionally substituted by 1 to 2
Ra independently selected groups; and

[0249](5) if two adjacent groups selected from R6, R7, R8,
R9, and R10, along with the carbons to which they are attached,
form a fused phenyl ring or a 5- or 6-membered heteroaryl ring, each of
which is optionally substituted by 1 to 2 Rb independently selected
groups; then: (a) the remaining R6, R7, R3, R9, and
R10 groups are not selected from C3-6 cycloalkyl, phenyl, a 5-
or 6-membered heteroaryl ring, and a 5- or 6-membered hetercycloalkyl
ring; and (b) the remaining R6, R7, R3, R9, and
R10 adjacent groups, along with the carbons to which they are
attached, do not form a fused phenyl ring or a 5- or 6-membered
heteroaryl ring, each of which is optionally substituted by 1 to 2
Rb independently selected groups.

[0250]The ligand is formed after hydrolysis of any hydrolysable groups for
R1, R2, R3, R4, R5, R6, R7, R8,
R9, and R10, such as C1-4 alkylcarbonyloxy, C1-4
haloalkylcarbonyloxy, C1-4 alkyloxycarbonyl, C1-4
haloalkyloxycarbonyl, tri(C1-4 allyl)silyloxy, or tri(C1-4
haloalkyl)silyloxy; or C1-4 alkylene substituted by a moiety
selected from C1-4 alkylcarbonyloxy, C1-4 haloalkylcarbonyloxy,
C1-4 alkyloxycarbonyl, and C1-4 haloalkyloxycarbonyl. This
mixture forms during the Suzuki polymerization processes of the
invention. In some embodiments, the mixture further comprises an organic
solvent.

Preparation of the Palladium Complexes

[0251]The ligands and complexes of the present invention can be prepared
in a variety of ways known to one skilled in the art of organic
synthesis. The compounds of the present invention can be synthesized
using the methods as hereinafter described below, together with synthetic
methods known in the art of synthetic organic chemistry or variations
thereon as appreciated by those skilled in the art.

[0252]The ligands and complexes of present invention can be conveniently
prepared in accordance with the procedures outlined in the schemes below,
from commercially available starting materials, compounds known in the
literature, or readily prepared intermediates, by employing standard
synthetic methods and procedures known to those skilled in the art.
Standard synthetic methods and procedures for the preparation of organic
molecules and functional group transformations and manipulations can be
readily obtained from the relevant scientific literature or from standard
textbooks in the field. It will be appreciated that where typical or
preferred process conditions (i.e., reaction temperatures, times, mole
ratios of reactants, solvents, pressures, etc.) are given, other process
conditions can also be used unless otherwise stated. Optimum reaction
conditions may vary with the particular reactants or solvent used, but
such conditions can be determined by one skilled in the art by routine
optimization procedures. Those skilled in the art of organic synthesis
will recognize that the nature and order of the synthetic steps presented
may be varied for the purpose of optimizing the formation of the
compounds of the invention.

[0253]In some embodiments, the processes described herein are monitored
according to any suitable method known in the art. For example, product
formation can be monitored by spectroscopic means, such as nuclear
magnetic resonance spectroscopy (e.g., 1H or 13C NMR) infrared
spectroscopy, spectrophotometry (e.g., IN-visible), or mass spectrometry,
or by chromatography such as high performance liquid chromatography
(HPLC) or thin layer chromatography.

[0254]Preparation of compounds can involve the protection and deprotection
of various chemical groups. The need for protection and deprotection, and
the selection of appropriate protecting groups can be readily determined
by one skilled in the art. The chemistry of protecting groups can be
found, for example, in Greene, et al., Protective Groups in Organic
Synthesis, 4th. Ed., Wiley & Sons, 2007, which is incorporated herein by
reference in its entirety.

[0255]The reactions of the processes described herein can be carried out
in suitable solvents which can be readily selected by one of skill in the
art of organic synthesis. Suitable solvents can be substantially
nonreactive with the starting materials (reactants), the intermediates,
or products at the temperatures at which the reactions are carried out,
i.e., temperatures which can range from the solvent's freezing
temperature to the solvent's boiling temperature. A given reaction can be
carried out in one solvent or a mixture of more than one solvent.
Depending on the particular reaction step, suitable solvents for a
particular reaction step can be selected.

[0256]There are a number of synthetic procedures for making many dba
ligands with different substitutents. Additionally, dba ligands can be
prepared by the following general method by an aldol condensation of an
aldehyde with acetone such as shown in Scheme A below. In some
embodiments, the dba ligand is made by an acid catalyzed route.
Asymmetric dba ligands of Formula la can be made by carefully controlling
the stoichiometry, such as in the methods in Tenkovtsev, A. V.;
Yakimansky, A. V.; Dudkina, M. M.; Lukoshkin, V. V.; Komber, H.;
Haussler, L.; Bohme, F. Macromolecules, 2001, 34, 7100-7107. There are
many known benzaldehydes which have been prepared in the literature, as
well as a number of commercially available benzaldehydes with a variety
of substitution patterns.

##STR00013##

[0257]Modifications can be made to the functional groups in a variety of
ways. For example, quaternary ammonium derivatives can be made by
quaternizing the amino group of a dba synthesized from an
aminobenzaldehyde derivative (e.g., see the scheme below). Commercially
available aminobenzaldehyde derivatives that can be quaternized in this
manner include 2-aminobenzaldehyde,
2-methyl-N-ethyl-N-(2-cyanoethyl)-4-aminobenzaldehyde,
N-methyl-N-(2-hydroxyethyl)-4-aminobenzaldehyde,
4-[N,N-bis(2-hydroxyethyl)amino]benzaldehyde,
4-(dimethylamino)benzaldehyde, and 4-dimethylamino-2-methoxybenzaldehyde.

##STR00014##

[0258]Placement of a sulfate group can be accomplished by oxidation of the
a methylthio group, starting from a commercially available or synthesized
alkyl-thio benzaldehyde derivative. For example, a sulfate compound can
be synthesized from 4-(methylthio)benzaldehyde (e.g., see scheme below).
Alternatively, the electron-poor alkenylketone should activate a
chlorinated dba towards SNAr chemistry as shown in the second scheme
below. The chlorinated dba derivatives are synthesized in the usual
manner from chlorobenzaldehyde derivitves, many of which are commercially
available, including 4-amino-2-chloro-benzaldehyde,
3-Chloro-2-fluoro-5-(trifluoromethyl)benzaldehyde,
3-Chloro-2-fluoro-6-(trifluoromethyl)benzaldehyde,
2-Chloro-3-(trifluoromethyl)benzaldehyde,
2-Chloro-5-(trifluoromethyl)benzaldehyde,
4-Chloro-3-(trifluoromethyl)benzaldehyde,
2-(4-chloro-3-methyl-phenoyxmethyl)-4-methoxybenzaldehyde,
3-chloro-hydroxy-5-methoxybenzaldehyde, 3-(4-Chlorophenyl)benzaldehyde,
2-Chlorobenzaldehyde, 3-Chlorobenzaldehyde, 4-Chlorobenzaldehyde,
2-Chloro-6-methylbenzaldehyde, 2-Chloro-4-hydroxybenzaldehyde,
2-Chloro-3-hydroxybenzaldehyde, 2-Chloro-6-fluorobenzaldehyde,
2-Chloro-4-fluorobenzaldehyde, 2-Chloro-3-methoxybenzaldehyde,
6-Chloro-2-fluoro-3-methylbenzaldehyde,
2-Chloro-6-fluoro-3-methylbenzaldehyde,
2-Chloro-3,6-difluorobenzaldehyde, 6-chloropiperonal,
2-Chloro-6-nitrobenzaldehyde, 2-Chloro-5-nitrobenzaldehyde,
2-Chloro-3-hydroxy-4-methoxybenzaldehyde,
2-Chloro-3,4-dimethoxybenzaldehyde, 3-Chloro-4-methylbenzaldehyde,
3-Chloro-2-hydroxybenzaldehyde, 3-Chloro-4-hydroxybenzaldehyde,
5-Chlorosalicylaldehyde, 3-Chloro-2-fluorobenzaldehyde,
3-chloro-5-fluorobenzaldehyde, 3-Chloro-4-fluorobenzaldehyde,
3-Chloro-4-methoxybenzaldehyde, 3-Chloro-5-fluorosalicylaldehyde,
3-Chloro-5-fluoro-4-hydroxybenzaldehyde,
3-Chloro-2,6-difluorobenzaldehyde, 5-Chloro-2-nitrobenzaldehyde,
4-Chloro-3-Fluorobenzaldehyde, 2,4-dichlorobenzaldehyde,
3,4-dichlorobenzaldehyde, 4-chloro-3-nitrobenzaldehyde, and
4-chloro-2-nitrobenzaldehyde.

##STR00015##

[0259]Sulfinate salts could be achieved by oxidizing the mercaptans, which
in turn can be isolated via SNAr chemistry. The chlorinated dba
derivatives are synthesized in the usual manner from chlorobenzaldehyde
derivitves, many of which are commercially available (see above).

[0261]The compounds of Formula Ia having an C1-4 alkylene spacer
could be synthesized by treating the methyl derivative with NBS, and then
substituting with cyanide (subsequent hydrolysis yields the acid,
sulfite, or a phosphite.

[0262]Carboxyl containing dbas can be synthesized through aldol
condensation starting from formylbenzoic acid derivatives such as
4-formylbenzoic acid which is commercially available, Aldol condensation
in the usual manner should form the carboxyl-substituted dba.
Alternatively, a carboxyl group can be introduced via the organolithium.
The organolithium is synthesized from the bromide derivative, which comes
from a bromobenzaldehyde compound, many of which are commercially
available, as summarized above.

[0266]The palladium complexes of the invention are made by methods for
preparing a palladium dba complex. For example, the palladium complexes
may be prepared by reacting the dba ligand of Formula Ia with
palladium(II), generally palladium chloride in the presence of oxygen,
sodium acetate, in a methanol solvent at temperatures around 50°
C., as shown in the scheme below.

##STR00019##

[0267]The palladium complexes of the invention wherein L1 is a
phosphine ligand can be prepared by the methods shown in the schemes
below and as described in Paul, F.; Patt, J.; Hartwig, J. F.
Organometollics, 1995, 14, 3030-3039. Depending upon the phosphine,
L1Pd(dba)2 or L1Pd(dba) can be formed preferentially
(wherein dba is the ligand of Formula Ia).

##STR00020##

[0268]The palladium complexes of the invention wherein L1 is a
phosphine equivalent such as a N-heterocyclic carbene ("NHC") ligand (e.
g. that generated in situ from 1,3-bis(2,4,6-trimethylphenyl)imidazolium
chloride or other salt thereof, or generated in situ form
1,3-bis(2,6-diisopropylphenyl)imidizolium chloride or other salt
thereof), could be forming the phosphine equivalent in situ, e.g., from
the imdazolium chloride salt, by treating it with a base like alkoxide.
The complex could be prepared by a method analogous to Hartwig's
procedure for preparing the analogous phosphine complexes. The reaction
should be performed in THF to keep the complex soluble, in the presence
of a base that is insoluble in THF to prevent deprotonation of the
hydroxy-dba ligand. The imidazolium chloride is suspended in THF along
with an excess of NaH. After stirring for 15 minutes, the suspension is
filtered to remove excess base. This filtered solution is then added to a
THE solution of the palladium complex (NHC:Pd molar ratio of 2:1), and
the reaction is allowed to stir for 24 hours. After filtration,
crystallization can be induced by layering two volumes of diethyl ether
onto the solution. An NHC-Pd-(dba) complex has been postulated as an
intermediate in a Suzuki coupling of aryl chlorides: Fairlamb, I. J. S.;
Kapdi, A. R.; Lee, A. F.; McGlacken, G. P.; Weissburger, F.; de Vries, A.
H. M.; Schmieder-van de Vondervoort, L. Chem. Eur. J. 2006, 12,
8750-8761.

EXAMPLES

[0269]In order that the invention disclosed herein may be more efficiently
understood, examples are provided below. It should be understood that
these examples are for illustrative purposes only and are not to be
construed as limiting the invention in any manner.

Example 1

Screening of palladium Catalysts

[0270]The catalyst systems for Suzuki coupling reactions generally consist
of a palladium source and a phosphine cocatalyst. These react rapidly in
situ to form palladium-phosphine complexes, which are believed to be the
actual catalysts in the catalytic cycle (Scheme 1). Most of the work in
catalyst development has been geared towards the synthesis and screening
of new phosphine cocatalysts. By tuning the sterics and electronics of
these ligands, researchers have been able to amp up the activities of the
resulting catalysts in small molecule coupling reactions.

[0271]Unfortunately, when used in polymerization, the new cocatalysts do
not provide molecular weight improvements when compared to the values
obtained with a traditional system. One surprising result, however, was
that the molecular weights were strongly dependent upon the source of
palladium used in the polymerizations. Murage, J.; Eddy, J. W.;
Zimbalist, J. R.; McIntyre, T. B.; Wagner, Z. R.; Goodson, F. E.,
Macromolecules, 2008, 41, 7330-7338. This not only calls into doubt the
above assumptions on the identity of the catalytically active species,
but it also suggests that in tuning the properties of the phosphine
cocatalyst, researchers have been attempting to optimize the wrong
component of the catalyst system.

##STR00021##

[0272]One of the most common sources of palladium in Suzuki coupling
reactions is tris(dibenzylideneacetone)dipalladium(0), or
Pd2dba3. This compound has the advantageous properties of being
soluble and air-stable, and it is known to react rapidly with phosphines
and aryl halides for expedient entry into the catalytic cycle (eq. 3).
However, from extensive electrochemical studies on palladium phosphine
complexes, the dibenzylideneacetone (dba) byproducts released from this
catalyst induction step are actually stronger ligands than phosphines.
Amatore, C.; Jutand, A., in Handbook of Organopalladium Chemistry for
Organic Synthesis, Negishi, E., Ed.; John Wiley & Sons, Inc.: Hoboken,
N.J., 2002; Vol. 1, p. 943-972. This may suggest that the dba ligands
should be intimately involved in the catalytic cycle, rather than serve
as benign spectators--a supposition that would explain the fact that we
have found that molecular weights were strongly dependent upon the source
of palladium used in the polymerizations.

##STR00022##

[0273]In an attempt to optimize the molecular weights of polymers
synthesized using Suzuki coupling, a number of palladium catalysts were
synthesized and screened in polymerization reactions. Simultaneous
polymerizations (eq. 2, n=6, m=1) were set up with precursors A, B, C, D,
and E (Table 1). As can be seen from the data in Table 2, the
electron-rich complex A preformed worse than the electron-neutral complex
C, which performed worse than the electron-poor complex B. While our
results did confirm that the molecular weights could be varied with the
choice of the dba ligand on the catalyst precursor, none of the new
systems matched the molecular weights obtained with E.

[0275]Unfortunately, the use of E as a catalyst is highly inconvenient.
For example, its purification may require a weeks-long recrystallization
for full recovery (Paul, F.; Patt, J.; Hartwig, J. F., Organometallics
1995, 14, 3030-3039). Further, since it is sensitive to heat, light, and
oxygen, it has to be stored in a drybox freezer and manipulated in an
oxygen-free atmosphere. Ideally, a catalyst system will combine the
convenience and stability of Pd2dba3 with the activity of E. A
dba ligand that would deliver the palladium into the catalytic cycle
(thus forming E in situ) without interfering with the subsequent
catalysis would provide such a system.

[0276]Towards this end, palladium complex F was synthesized (eq. 5) from
the readily obtained ligand. The dibenzylideneacetone ligand is
synthesized by reacting acetone and 4-hydroxybenzaldehyde under
acid-catalyzed conditions (eq. 4, HCl used as the acid, in methanol).
This synthesis and subsequent purification were performed in air,
verifying the air stability of this complex. Unambiguous characterization
of F was achieved by isolating structure-quality crystals, which were
then analyzed via X-ray crystallography (FIG. 1).

##STR00025##

[0277]Without wishing to be bound by a particular theory, is is believed
that, for F, that the basic conditions of the catalysis cause the
phenolic proton of the ligand to be deprotonated, thus turning the
moderately electron-donating hydroxy group into a strongly donating oxide
(Scheme 3). Evidence for the deprotonation (and subsequent aqueous
partitioning) of 1 during the polymerization was provided by the fact
that the aqueous phase turned orange as the reaction progressed. Since we
think that strongly electron-donating groups on the dba ligands do not
provide for stable complexes, we believed this pH switch may turn a
strong Pd(0) ligand into a weak one. Furthermore, the negative charge on
the phenoxide groups may cause the dba ligands to partition into the
aqueous phase, allowing the catalysis to occur unhindered in the organic
phase. As can be seen from the data in Table 1, we obtained molecular
weights with F comparable (at the high end) to those of E, and far
surpassing (even at the low end) those obtained with the other
Pd2dba3 complexes.

##STR00026##

[0278]One disadvantage of F is that it is not soluble in the
CH2Cl2 solvent system that was found to be optimal for these
polymerizations. To work around this difficulty, an acetyl complex G was
synthetized from the corresponding dba 2 (equation 6, obtained by
acetylating 1 in acetic anhydride). The acetyl group provided a greater
amount of solubility, while the base lability allowed for G to be
transformed into F under the basic conditions of the polymerization. As
can be seen from the data in Table 2, G did perform better than A, B, and
C. However, the molecular weights were not as high as those obtained with
the best ran from F (although these polymerizations also turned orange).
Use of a more base-labile protecting group, such as chloroacetate,
dichloroacetate, trichloroacetate, or trifluoroacetate should allow for
more efficient removal of the protecting group at the beginning of the
polymerization.

##STR00027##

[0279]Complex D, the catalyst system most commonly used in Suzuki
polycondensations, was not initially screened, since
triphenylphosphine-based catalysts are known to be incompatible with
halogenated solvents (Goodson, F. E.; Wallow, T. I.; Novak, B. M., J. Am.
Chem. Soc. 1997, 119, 12441-12453; Grushin, V. V., Organometallics 2000,
19, 1888-1900.). Thus, in order to compare our systems more fairly with
the traditional examples, polymerizations with C, D, E, and F were also
performed in THF (Table 1). While D did result in molecular weights that
were consistent with its use in the literature (e. g. Zhou, X.-H.; Zhang,
Y.; Xie, Y.-Q.; Cao, Y.; Pei, J., Macromolecules 2006, 39, 3830-3840),
the results were still inferior to those of the
tri(o-tolyl)phosphine-based systems (in agreement with literature
observations: Goodson, F. E.; Wallow, T. I,; Novak, B. M., Macromolecules
1998, 31, 2047-2056). Interestingly, the performance of F was not as
impressive in this solvent, yielding results that, while still superior
to C, were noticeably inferior to those of E. This indicates to us that a
hydrophobic cosolvent, such as CH2Cl2, is preferred for better
partitioning of 1 into the aqueous phase, thus preventing it from
interfering with the catalysis.

[0282]Palladium complexes C and D as well as tri(o-tolyl)phosphine
(obtained air-free from commercial suppliers) were stored and weighed out
in an argon-filled drybox. Polymerization solvents were obtained air-free
and anhydrous from Aldrich, and were similarly stored and dispensed in
the drybox. All other chemicals, including penta(ethylene
glycol)di(p-toluenesulfonate), were used as received from commercial
suppliers. The water content for commercial K3PO4.xH2O
varies from sample to sample, and that for the particular sample used was
determined to be 19% from TGA and titration experiments. Molecular
weights were measured in chloroform solution with a tandem GPC-LS
apparatus that consisted of an Agilent Technologies Series 1100 or
Perkin-Elmer Series 200 EPLC pump equipped with Waters Styrogel GPC
columns (HR5E, HR4, HR4E connected in series) in line with a Wyatt
Technologies DAWN-EOS light scattering photometer and a Wyatt Optilab DSP
interferometic refractometer. Measurements were made at 25.0° C.
and a wavelength of 690 nm.

[0285]A 100 mL round-bottomed flask was charged with 0.928 g (11.3 mmol)
of anhydrous sodium acetate, 1.24 g (4.66 mmol) of 1, 35 mL of methanol,
and a magnetic stirbar. The flask was placed in a 50° C. oil bath,
and after 15 minutes, 0.25 g (1.41 mmol) of palladium chloride was added.
The mixture was allowed to stir in open air at 50° C. for four
hours. The reaction was then poured into 100 mL of water, and the
resulting precipitate was isolated via vacuum filtration. After rinsing
well with water and diethyl ether, the crude product was dried in vacuo.
This was the crude powder used in entries 8-9 of Table 2 (Examples 15 and
16). It was then taken up in 20 mL of THF, filtered through a pad of
diatomaceous earth, and recrystallized by layering 30 mL of diethyl ether
onto the filtered THF solution. After 24 h at room temperature, the
resulting crystals were isolated via vacuum filtration, rinsed with
diethyl ether, and dried in vacuo to yield 0.124 g (0.246 mmol Pd, 17.4%)
of F as a dark purple powder crystalline mass. A sample of this was taken
up in 1 mL of oxygen-free dioxane, filtered through diatomaceous earth,
frozen, and then placed under vacuum overnight to freeze-dry the sample
and produce the purified powder.

Example 5

4,4'-Diacetoxydibenzylideneacetone (2)

[0286]A 100 mL round-bottomed flask was charged with 0.971 g (3.65 mmol)
of 1, 50 mL of acetic anhydride and a stirbar. The flask was fitted with
a reflux condenser, and the reaction was brought to reflux for several
hours. Afterwards, it was poured into 100 mL of water, resulting in the
precipitation of a yellow solid. This was removed via vacuum filtration,
after which it was recrystallized from ethanol resulting in the isolation
of 0.951 g (2.72 mmol, 74.4%) of 2 as yellow needles.

Example 6

Tris[4,4'-diacetoxydibenzylideneacetone)dipalladium(0) (G)

[0287]A 100 mL round-bottomed flask was charged with 0.465 g (5.67 mmol)
of anhydrous sodium acetate, 0.820 g (2.34 mmol) of 2, 18 mL of methanol,
and a magnetic stirbar. The flask was placed in a 50° C. oil bath,
and after 15 minutes, 0.125 g (0.705 mmol) of palladium chloride was
added. The mixture was allowed to stir in open air at 40° C. for
four hours. The reaction was then allowed to cool to room temperature,
and the resulting precipitate was isolated via vacuum filtration. After
rinsing well with water and methanol, the crude product was dried in
vacuo. It was then taken up in 40 mL of boiling chloroform, filtered
while still hot through a pad of diatomaceous earth, and recrystallized
by layering 20 mL of diethyl ether onto the cooled, filtered chloroform
solution. After a week at room temperature, the resulting crystals were
isolated via vacuum filtration, rinsed with diethyl ether, and dried in
vacuo to yield 0.113 g (0.179 mmol Pd, 25.3%) of G as a dark purple
powder.

Example 7

Polymerizations

[0288]Initial studies with F were carried out on the crude powder isolated
before recrystallization (entries 8 and 9). As shown in the table
results, compared favorably to E and to the standard system involving C.
However, as this material was not free of contaminates, it was later
purified by recrystallization from THF and diethyl ether. While the
crystalline form worked well in THF (entries 17-18), in which F is
soluble, it performed poorly in CH2Cl2 (the preferred
polymerization solvent), in which F is insoluble (entries 19-20).
However, this solubility hurdle can be overcome by freeze-drying F from
dioxane, thus generating a pure powder which again produced good results
(entries 25-26). Alternatively, complex G, in which the hydroxyl groups
are protected as the acetates, is soluble in CH2Cl2. As these
dba ligands are released into the medium, the acetate groups are removed
under the basic conditions, and the resulting phenoxides partition into
the aqueous phase. This system produced results (entries 10, 11, 28, 29)
only slightly inferior to those of F. In all cases, G and the powdered
form of F (crude or freeze-dried) outperformed the standard system
derived from C. However, they did not match the performance of E, which
remains the best catalyst system we have screened to date. Conceivably,
powdered F could more closely mimic E by undergoing a pre-reaction with
the monomers and phosphine (thus permitting the palladium to enter the
catalytic cycle prior to polymerization). In order to accomplish this, a
polymerization was set up in which F was allowed to react with the
monomers and phosphine in THF for 15 minutes, after which the solvent was
removed in vacuo. The polymerization solvent (CH2Cl2) and base
were then added in the usual manner. However, as shown in entry 27, the
results did not differ appreciably from those obtained with powdered F
introduced as per usual.

[0289]To each of several 10 mL ampoules was added 0.500 mL of a
CH2Cl2 stock solution 0.3 M in hexaethylene glycol
di(3-bromophenyl)ether and 1,4-bis(1,3,2-dioxaborolan-2-yl)benzene
monomers. Solvent was removed in vacuo after which the ampoules were
back-filled with nitrogen, capped, wax-sealed, and stored at -10°
C. in the dark until ready for use. Polymerizations were set up 6-12 at a
time by charging the ampoules with stirbars along with the appropriate
palladium source, 0.300 mL of degassed 3M aqueous K3PO4,
phosphine cocatalyst (if required) and enough additional solvent so that
each tube contained 0.150 mL of organic solvent and 0.300 mL of aqueous
solution. The vessels were degassed via three freeze-pump-thaw cycles,
sealed under vacuum, and placed in a thermostatted 50° C. water
bath over an efficient magnetic stirrer for three days. The resulting
materials were taken up in a minimal amount of CHCl3 spiked with
aliquat (2 drops per 100 mL), transferred to centrifuge tubes, extracted
with 5% aqueous NaCN (1 mL) and washed 6 times with 1 mL of HPLC-grade
water. The organic phases were transferred to separate scintillation
vials (no drying agent was used), after which the solvent was removed
with a rotary evaporator. The resulting films were then dried at
100° C. under a 1 mtorr vacuum for 20 minutes, and analyzed via
GPC-LS without further purification.

[0290]To each of several 10 mL ampoules was added 0.500 mL of a
CH2Cl2 stock solution 0.3 M in pentaethylene glycol
di(3-bromophenyl)ether and 1,4-bis(1,3,2-dioxaborolan-2-yl)benzene
monomers. Solvent was removed in vacuo after which the ampoules were
back-filled with nitrogen, capped, wax-sealed, and stored at -10°
C. in the dark until ready for use. Polymerizations were set up 6-12 at a
time by charging the ampoules with stirbars along with the appropriate
palladium source, 0.300 mL of degassed 3M aqueous K3PO4,
phosphine cocatalyst (if required) and enough additional solvent so that
each tube contained 0.150 mL of organic solvent and 0.300 mL of aqueous
solution. The vessels were degassed via three freeze-pump-thaw cycles,
sealed under vacuum, and placed in a thermostatted 50° C. water
bath over an efficient magnetic stirrer for three days. The resulting
materials were taken up in a minimal amount of CHCl3 spiked with
aliquat (2 drops per 100 mL), transferred to centrifuge tubes, extracted
with 5% aqueous NaCN (1 mL) and washed 6 times with 1 mL of HPLC-grade
water. The organic phases were transferred to sealable microwave reaction
tubes, after which they were heated to 150 degrees for fifteen minutes in
a microwave pressure reactor. This procedure was sometimes required for
complete dissolution of the material. Afterwards, the resulting solutions
were stirred overnight with 5 mL of HPLC-grade water. The aqueous phases
were then removed, and the chloroform solutions were transferred to
separate scintillation vials (no drying agent was used), after which the
solvent was removed with a rotary evaporator. The resulting films were
then dried at 100° C. under a 1 mtorr vacuum for 20 minutes, and
analyzed via GPC-LS without further purification.

Example 8

Table 2, Entry 1

[0291]A stock solution 0.04 M in tri(o-tolyl)phosphine was prepared by
dissolving 12.2 mg (0.0400 mmol) of the ligand in 1.0 mL oxygen-free
CH2Cl2. An ampoule pre-loaded with 0.150 mmol of each monomer
was then charged with a stirbar, 1.8 mg (0.003 mmol Pd) of A, 75 μL of
the phosphine stock (0.0030 mmol), 75 μL of degassed CH2Cl2,
and 300 μL of degassed 3M aqueous K3PO4. The polymerization
was then set up and worked up as described above, to provide 72.2 mg
(94.8%) of the crude polymer as a filmy material.

Example 9

Table 2, Entry 2

[0292]A stock solution 0.04 M in tri(o-tolyl)phosphine was prepared by
dissolving 12.2 mg (0.0400 mmol) of the ligand in 1.0 mL oxygen-free
CH2Cl2. An ampoule pre-loaded with 0.150 mmol of each monomer
was then charged with a stirbar, 2.2 mg (0.003 mmol Pd) of B, 75 μL of
the phosphine stock (0.0030 mmol), 75 μL of degassed CH2Cl2,
and 300 μL of degassed 3M aqueous K3PO4. The polymerization
was then set up and worked up as described above, to provide 42.7 mg
(56.0%, some mechanical loss) of the crude polymer as a filmy material.

Example 10

Table 2, Entry 3

[0293]A stock solution 0.04 M in tri(o-tolyl)phosphine was prepared by
dissolving 12.2 mg (0.0400 mmol) of the ligand in 1.0 mL oxygen-free
CH2Cl2. An ampoule pre-loaded with 0.150 mmol of each monomer
was then charged with a stirbar, 2.2 mg (0.003 mmol Pd) of B, 75 μL of
the phosphine stock (0.0030 mmol), 75 μL of degassed CH2Cl2,
and 300 μL of degassed 3M aqueous K3PO4. The polymerization
was then set up and worked up as described above, to provide 83.0 mg
(109%) of the crude polymer as a filmy material.

Example 11

Table 2, Entry 4

[0294]A stock solution 0.04 M in tri(o-tolyl)phosphine was prepared by
dissolving 12.2 mg (0.0400 mmol) of the ligand in 1.0 mL oxygen-free
CH2Cl2. An ampoule pre-loaded with 0.150 mmoL of each monomer
was then charged with a stirbar, 1.4 mg (0.003 mmol Pd) of C, 75 μL of
the phosphine stock (0.0030 mmoL), 75 μL of degassed CH2Cl2,
and 300 μL of degassed 3M aqueous K3PO4. The polymerization
was then set up and worked up as described above, to provide 76.7 mg
(101%) of the crude polymer as a filmy material.

Example 12

Table 2, Entry 5

[0295]An ampoule pre-loaded with 0.150 mmol of each monomer was then
charged with a stirbar, 1.1 mg (0.0015 mmol Pd) of E, 150 μL of
degassed CH2Cl2, and 300 μL of degassed 3M aqueous
K3PO4. The polymerization was then set up and worked up as
described above, to provide 85.6 mg (112%) of the crude polymer as a
filmy material.

Example 13

Table 2, Entry 6

[0296]An ampoule pre-loaded with 0.150 mmol of each monomer was then
charged with a stirbar, 1.1 mg (0.0015 mmol Pd) of E, 150 μL of
degassed CH2Cl2, and 300 μL of degassed 3M aqueous
K3PO4. The polymerization was then set up and worked up as
described above, to provide 81.1 mg (106%) of the crude polymer as a
filmy material.

Example 14

Table 2, Entry 7

[0297]An ampoule pre-loaded with 0.150 mmol of each monomer was then
charged with a stirbar, 1.1 mg (0.0015 mmol Pd) of E, 150 μL of
degassed CH2Cl2, and 300 μL of degassed 3M aqueous
K3PO4. The polymerization was then set up and worked up as
described above, to provide 84.6 mg (111%) of the crude polymer as a
filmy material.

Example 15

Table 2, Entry 8

[0298]A stock solution 0.04 M in tri(o-tolyl)phosphine was prepared by
dissolving 12.2 mg (0.0400 mmol) of the ligand in 1.0 mL oxygen-free
CH2Cl2. An ampoule pre-loaded with 0.150 mmol of each monomer
was then charged with a stirbar, 1.5 mg (0.003 mmol Pd) of F, 75 μL of
the phosphine stock (0.0030 mmol), 75 μL of degassed CH2Cl2,
and 300 μL of degassed 3M aqueous K3PO4. The polymerization
was then set up and worked up as described above, to provide 90.4 mg
(115%) of the crude polymer as a filmy material.

Example 16

Table 2, Entry 9

[0299]A stock solution 0.04 M in tri(o-tolyl)phosphine was prepared by
dissolving 12.2 mg (0.0400 mmol) of the ligand in 1.0 mL oxygen-free
CH2Cl2. An ampoule pre-loaded with 0.150 mmol of each monomer
was then charged with a stirbar, 1.5 mg (0.003 mmol Pd) of F, 75 μL of
the phosphine stock (0.0030 mmol), 75 μL of degassed CH2Cl2,
and 300 μL of degassed 3M aqueous K3PO4. The polymerization
was then set up and worked up as described above, to provide 76.8 mg
(101%) of the crude polymer as a filmy material.

Example 17

Table 2, Entry 10

[0300]A stock solution 0.04 M in tri(o-tolyl)phosphine was prepared by
dissolving 12.2 mg (0.0400 mmol) of the ligand in 1.0 mL oxygen-free
CH2Cl2. An ampoule pre-loaded with 0.150 mmol of each monomer
was then charged with a stirbar, 1.9 mg (0.003 mmol Pd) of G, 75 μL of
the phosphine stock (0.0030 mmol), 75 μL of degassed CH2Cl2,
and 300 μL of degassed 3M aqueous K3PO4. The polymerization
was then set up and worked up as described above, to provide 98.3 mg
(129%) of the crude polymer as a filmy material.

Example 18

Table 2, Entry 11

[0301]A stock solution 0.04 M in tri(o-tolyl)phosphine was prepared by
dissolving 12.2 mg (0.0400 mmol) of the ligand in 1.0 mL oxygen-free
CH2Cl2. An ampoule pre-loaded with 0.150 mmol of each monomer
was then charged with a stirbar, 1.9 mg (0.003 mmol Pd) of G, 75 μL of
the phosphine stock (0.0030 mmol), 75 μL of degassed CH2Cl2,
and 300 μL of degassed 3M aqueous K3PO4. The polymerization
was then set up and worked up as described above, to provide 83.6 mg
(110%) of the crude polymer as a filmy material.

Example 19

Table 2, Entry 12

[0302]A stock solution 0.04 M in tri(o-tolyl)phosphine was prepared by
dissolving 12.2 mg (0.0400 mmol) of the ligand in 1.0 mL oxygen-free THF.
An ampoule pre-loaded with 0.150 mmol of each monomer was then charged
with a stirbar, 1.4 mg (0.003 mmol Pd) of C, 150 μL of the phosphine
stock (0.0060 mmol), and 300 μL of degassed 3M aqueous
K3PO4. The polymerization was then set up and worked up as
described above, to provide 75.8 mg (99.5%) of the crude polymer as a
filmy material.

Example 20

Table 2, Entry 13

[0303]A stock solution 0.04 M in tri(o-tolyl)phosphine was prepared by
dissolving 12.2 mg (0.0400 mmol) of the ligand in 1.0 mL oxygen-free THF.
An ampoule pre-loaded with 0.150 mmol of each monomer was then charged
with a stirbar, 1.4 mg (0.003 mmol Pd) of C, 150 μL of the phosphine
stock (0.0060 mmol), and 300 μL of degassed 3M aqueous
K3PO4. The polymerization was then setup and worked up as
described above, to provide 85.3 mg (112%) of the crude polymer as a
filmy material.

Example 21

Table 2, Entry 14

[0304]An ampoule pre-loaded with 0.150 mmol of each monomer was then
charged with a stirbar, 3.5 mg (0.003 mmol Pd) of D, 150 μL of
degassed THF, and 300 μL of degassed 3M aqueous K3PO4. The
polymerization was then set up and worked up as described above, to
provide 81.9 mg (107%) of the crude polymer as a filmy material.

Example 22

Table 2, Entry 15

[0305]An ampoule pre-loaded with 0.150 mmol of each monomer was then
charged with a stirbar, 2.1 mg (0.003 mmol Pd) of E, 150 μL of
degassed THF, and 300 μL of degassed 3M aqueous K3PO4. The
polymerization was then set up and worked up as described above, to
provide 80.6 mg (106%) of the crude polymer as a filmy material.

Example 23

Table 2, Entry 16

[0306]An ampoule pre-loaded with 0.150 mmol of each monomer was then
charged with a stirbar, 2.1 mg (0.003 mmol Pd) of E, 150 μL of
degassed THF, and 300 μL of degassed 3M aqueous K3PO4. The
polymerization was then set up and worked up as described above, to
provide 77.8 mg (102%) of the crude polymer as a filmy material.

Example 24

Table 2, Entry 17

[0307]A stock solution 0.04 M in tri(o-tolyl)phosphine was prepared by
dissolving 12.2 mg (0.0400 mmol) of the ligand in 1.0 mL oxygen-free THF.
An ampoule pre-loaded with 0.150 mmol of each monomer was then charged
with a stirbar, 1.5 mg (0.003 mmol Pd) of F, 150 μL of the phosphine
stock (0.0060 mmol), and 300 μL of degassed 3M aqueous
K3PO4. The polymerization was then set up and worked up as
described above, to provide 81.3 mg (107%) of the crude polymer as a
filmy material.

Example 25

Table 2, Entry 18

[0308]A stock solution 0.04 M in tri(o-tolyl)phosphine was prepared by
dissolving 12.2 mg (0.0400 mmol) of the ligand in 1.0 mL oxygen-free THF.
An ampoule pre-loaded with 0.150 mmol of each monomer was then charged
with a stirbar, 1.5 mg (0.003 mmol Pd) of F, 150 μL of the phosphine
stock (0.0060 mmol), and 300 μL of degassed 3M aqueous
K3PO4. The polymerization was then set up and worked up as
described above, to provide 76.3 mg (100%) of the crude polymer as a
filmy material.

Example 26

Table 2, Entry 19

[0309]A stock solution 0.04 M in tri(o-tolyl)phosphine was prepared by
dissolving 24.4 mg (0.0400 mmol) of the ligand in 2 mL oxygen-free
CH2Cl2. An ampoule pre-loaded with 0.150 mmol of each monomer
was then charged with a stirbar, 1.5 mg (0.003 mmol Pd) of crystalline F,
150 μL of the phosphine stock (0.0060 mmol), and 300 μL of degassed
3M aqueous K3PO4. The polymerization was then set up and worked
up as described above, to provide 98.1 mg (129%) of the crude polymer as
a filmy material.

Example 27

Table 2, Entry 20

[0310]A stock solution 0.04 M in tri(o-tolyl)phosphine was prepared by
dissolving 24.4 mg (0.0400 mmol) of the ligand in 2 mL oxygen-free
CH2Cl2. An ampoule pre-loaded with 0.150 mmol of each monomer
was then charged with a stirbar, 1.5 mg (0.003 mmol Pd) of crystalline F,
150 μL of the phosphine stock (0.0060 mmol), and 300 μL of degassed
3M aqueous K3PO4. The polymerization was then set up and worked
up as described above, to provide 94.9 mg (129%) of the crude polymer as
a filmy material.

Example 28

Table 2, Entry 21

[0311]An ampoule pre-loaded with 0.150 mmol of each monomer was then
charged with a stirbar, 2.2 mg (0.0030 mmol Pd) of E, 150 μL of
degassed CH2Cl2, and 300 μL of degassed 3M aqueous
K3PO4. The polymerization was then set up and worked up as
described above, to provide 63.7 mg (91.5%) of the crude polymer as a
filmy material.

Example 28

Table 2, Entry 22

[0312]An ampoule pre-loaded with 0.150 mmol of each monomer was then
charged with a stirbar, 2.2 mg (0.0030 mmol Pd) of E, 150 μL of
degassed CH2Cl2, and 300 mL of degassed 3M aqueous
K3PO4. The polymerization was then setup and worked up as
described above, to provide 60.2 mg (86.5%) of the crude polymer as a
filmy material.

Example 29

Table 2, Entry 23

[0313]A stock solution 0.04 M in tri(o-tolyl)phosphine was prepared by
dissolving 24.4 mg (0.0400 mmol) of the ligand in 2 mL oxygen-free
CH2Cl2. An ampoule pre-loaded with 0.150 mmol of each monomer
was then charged with a stirbar, 1.4 mg (0.003 mmol Pd) of C, 150 μL
of the phosphine stock (0.0060 mmol), and 300 μL of degassed 3M
aqueous K3PO4. The polymerization was then set up and worked up
as described above, to provide 77.0 mg (111%) of the crude polymer as a
filmy material.

Example 30

Table 2, Entry 24

[0314]A stock solution 0.04 M in tri(o-tolyl)phosphine was prepared by
dissolving 24.4 mg (0.0400 mmol) of the ligand in 2 mL oxygen-free
CH2Cl2. An ampoule pre-loaded with 0.150 mmol of each monomer
was then charged with a stirbar, 1.4 mg (0.003 mmol Pd) of C, 150 μL
of the phosphine stock (0.0060 mmol), and 300 μL of degassed 3M
aqueous K3PO4. The polymerization was then set up and worked up
as described above, to provide 48.3 mg (69.4%) of the crude polymer as a
filmy material.

Example 31

Table 2, Entry 25

[0315]A stock solution 0.04 M in tri(o-tolyl)phosphine was prepared by
dissolving 24.4 mg (0.0400 mmol) of the ligand in 2 mL oxygen-free
CH2Cl2. An ampoule pre-loaded with 0.150 mmol of each monomer
was then charged with a stirbar, 1.5 mg (0.003 mmol Pd) of freeze-dried
F, 150 μL of the phosphine stock (0.0060 mmol), and 300 μL of
degassed 3M aqueous K3PO4. The polymerization was then set up
and worked up as described above, to provide 70.8 mg (102%) of the crude
polymer as a filmy material.

Example 32

Table 2, Entry 26

[0316]A stock solution 0.04 M in tri(o-tolyl)phosphine was prepared by
dissolving 24.4 mg (0.0400 mmol) of the ligand in 2 mL oxygen-free
CH2Cl2. An ampoule pre-loaded with 0.150 mmol of each monomer
was then charged with a stirbar, 1.5 mg (0.003 mmol Pd) of freeze-dried
F, 150 μL of the phosphine stock (0.0060 mmol), and 300 μL of
degassed 3M aqueous K3PO4. The polymerization was then set up
and worked up as described above, to provide 62.4 mg (89.7%) of the crude
polymer as a filmy material.

Example 33

Table 2, Entry 27

[0317]A stock solution 0.04 M in tri(o-tolyl)phosphine was prepared by
dissolving 24.4 mg (0.0400 mmol) of the ligand in 2 mL oxygen-free THF.
An ampoule pre-loaded with 0.150 mmol of each monomer was then charged
with a stirbar, 1.5 mg (0.003 mmol Pd) of freeze-dried F, and 150 μL
of the phosphine stock (0.0060 mmol). This mixture was allowed to stir
under nitrogen at room temperature for 15 minutes, after which the
solvent was removed in vacuo. Afterwards, 150 μL degassed
CH2Cl2 and 300 μL of degassed 3M aqueous K3PO4
were added via syringe. The polymerization was then set up and worked up
as described above, to provide 83.4 mg (120%) of the crude polymer as a
filmy material.

Example 34

Table 2, Entry 28

[0318]A stock solution 0.04 M in tri(o-tolyl)phosphine was prepared by
dissolving 24.4 mg (0.0400 mmol) of the ligand in 2 mL oxygen-free
CH2Cl2. An ampoule pre-loaded with 0.150 mmol of each monomer
was then charged with a stirbar, 1.9 mg (0.003 mmol Pd) of G, 150 μL
of the phosphine stock (0.0030 mmol), and 300 μL of degassed 3M
aqueous K3PO4. The polymerization was then set up and worked up
as described above, to provide 75.2 mg (108%) of the crude polymer as a
filmy material.

Example 35

Table 2, Entry 29

[0319]A stock solution 0.04 M in tri(o-tolyl)phosphine was prepared by
dissolving 24.4 mg (0.0400 mmol) of the ligand in 2 mL oxygen-free
CH2Cl2. An ampoule pre-loaded with 0.150 mmol of each monomer
was then charged with a stirbar, 1.9 mg (0.003 mmol Pd) of G, 150 μL
of the phosphine stock (0.0030 mmol), and 300 μL of degassed 3M
aqueous K3PO4. The polymerization was then set up and worked up
as described above, to provide 71.3 mg (102%) of the crude polymer as a
filmy material.

[0320]Various modifications of the invention, in addition to those
described herein, will be apparent to those skilled in the art from the
foregoing description. Such modifications are also intended to fall
within the scope of the appended claims. Each reference, including all
patent, patent applications, and publications, cited in the present
application is incorporated herein by reference in its entirety.

Patent applications in class Boron reactant contains a boron atom bonded to at least one atom of oxygen

Patent applications in all subclasses Boron reactant contains a boron atom bonded to at least one atom of oxygen